Dehydration reaction of hydroxyl substituted alkenes and alkynes on the Ru(2)S(2) complex

A variety of inter- and intramolecular dehydration was found in the reactions of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C(3)S(2) five-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CH(OCH(2)CH=CH(2))S]](CF(3)SO(3))(4) (2), via C-S bond formation after C-H bond activation and intermolecular dehydration. On the other hand, intramolecular dehydration was observed in the reaction of 1 with 3-buten-1-ol giving a C(4)S(2) six-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2) [mu-SCH(2)CH=CHCH(2)S]](CF(3)SO(3))(4) (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCR=CHCH(OCH(2)C triple bond CR)S]](CF(3)SO(3))(4) (4: R = H, 5: R = CH(3)), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OH)S]](CF(3)SO(3))(4) (6), was isolated, which further reacted with 2-propyn-1-ol and 2-butyn-1-ol to give 4 and a cross-coupling product, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OCH(2)C triple bond CCH(3))S]](CF(3)SO(3))(4) (7), respectively. The reaction of 1 with diols, (HO)CHRC triple bond CCHR(OH), gave furyl complexes, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SSC=CROCR=CH]](CF(3)SO(3))(3) (8: R = H, 9: R = CH(3)) via intramolecular elimination of a H(2)O molecule and a H(+). Even though (HO)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OH) does not have any propargylic C-H bond, it also reacts with 1 to give [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)C(=CH(2))C(=C=C(CH(3))(2))]S](CF(3)SO(3))(4) (10). In addition, the reaction of 1 with (CH(3)O)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OCH(3)) gives [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(2)][mu-S=C(C(CH(3))(2)OCH(3))C=CC(CH(3))CH(2)S][Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)]](CF(3)SO(3))(4) (11), in which one molecule of CH(3)OH is eliminated, and the S-S bond is cleaved.     

Insertion reactions into Pd[bond]O and Pd[bond]N bonds: preparation of alkoxycarbonyl,carbonato, carbamato,thiocarbamate, and thioureide complexes of palladium(II)

Mononuclear palladium hydroxo complexes of the type [Pd(N[bond]N)(C(6)F(5))(OH)] [(N[bond]N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N[bond]N)(C(6)F(5))(acetone)]ClO(4) with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)Me)]. Similar alkoxycarbonyl complexes [Pd(N[bond]N)(C(6)F(5))(CO(2)R)] (N[bond]N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or (i)Pr) are obtained when [Pd(N[bond]N)(C(6)F(5))Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N[bond]N)(C(6)F(5))(OH)] (N[bond]N = bipy or Me(2)bipy) with CO(2), in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N[bond]N)(C(6)F(5))Pd(mu-eta(2)-CO(3))Pd(C(6)F(5))(N[bond]N)]. Complexes [Pd(N[bond]N)(C(6)F(5))(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N[bond]N)(C(6)F(5))[SC(OR)NPh]]. Similarly, the reaction of [Pd(bipy)(C(6)F(5))(OH)] with PhNCO in methanol gives the N-phenyl-O-methylcarbamate complex [Pd(bipy)(C(6)F(5))[NPhC(O)OR]]. The reactions of [(N[bond]N)Pd(C(6)F(5))(OH)] with PhNCS in the presence of Et(2)NH yield the corresponding thioureidometal complexes [Pd(N[bond]N)(C(6)F(5))[NPhCSNR(2)]]. The crystal structures of [Pd(tmeda)(C(6)F(5))(CO(2)Me)], [Pd(2)(Me(2)bipy)(2)(C(6)F(5))(2)(mu-eta(2)-CO(3))].2CH(2)Cl(2), and [Pd(tmeda)(C(6)F(5))[SC(OMe)NPh]] have been determined.     

Ligand-modification effects on the reactivity, solubility, and stability of organometallic tantalum complexes in water

Tantalum complexes [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NMe(2))=CH)py}] (4) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NH(2))=CH)py}] (5), which contain modified alkoxide pincer ligands, were synthesized from the reactions of [TaCp*Me{κ(3)-N,O,O-(OCH(2))(OCH)py}] (Cp* = η(5)-C(5)Me(5)) with HC≡CCH(2)NMe(2) and HC≡CCH(2)NH(2), respectively. The reactions of [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(Ph)=CH)py}] (2) and [TaCp*Me{κ(4)-C,N,O,O-(OCH(2))(OCHC(SiMe(3))=CH)py}] (3) with triflic acid (1:2 molar ratio) rendered the corresponding bis-triflate derivatives [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(Ph)=CH(2))py}] (6) and [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(OCHC(SiMe(3))=CH(2))py}] (7), respectively. Complex 4 reacted with triflic acid in a 1:2 molar ratio to selectively yield the water-soluble cationic complex [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH)py}]OTf (8). Compound 8 reacted with water to afford the hydrolyzed complex [TaCp*(OH)(H(2)O){κ(3)-N,O,O-(OCH(2))(OCHC(CH(2)NHMe(2))=CH(2))py}](OTf)(2) (9). Protonation of compound 8 with triflic acid gave the new tantalum compound [TaCp*(OTf){κ(4)-C,N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH)py}](OTf)(2) (10), which afforded the corresponding protonolysis derivative [TaCp*(OTf)(2){κ(3)-N,O,O-(OCH(2))(HOCHC(CH(2)NHMe(2))=CH(2))py}](OTf) (11) in solution. Complex 8 reacted with CNtBu and potassium 2-isocyanoacetate to give the corresponding iminoacyl derivatives 12 and 13, respectively. The molecular structures of complexes 5, 7, and 10 were established by single-crystal X-ray diffraction studies.     

Facile allylic C-H bond activation on the bridging disulfide ligand in the Ru(III) dinuclear complex having a conjugated RuSSRu core

Treatment of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1), which is prepared by the reaction of [[RuCl(P(OCH(3))(3))(2)](2)(mu-S(2))(mu-Cl)(2)] (2) with 4 equiv of AgCF(3)SO(3), with terminal alkenes such as 1-pentene, allyl ethyl ether, allyl phenyl ether, 1,4-hexadiene, and 3-methyl-1-butene, resulted in the formation of complexes carrying a C(3)S(2) five-membered ring, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CR(1)R(2)S]](CF(3)SO(3))(4) (3, R(1) = CH(2)CH(3), R(2) = H, 40%; 4, R(1) = OCH(2)CH(3), R(2) = H, 60%; 5, R(1) = OC(6)H(5), R(2) = H, 73%; 6, R(1) = CH=CHCH(3), R(2) = H, 48%; 7, R(1) = R(2) = CH(3), 40%). Reaction of 1 with methylenecycloalkanes was found to give several different types of products, depending on the ring size of the substrates. A trace of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(CH(2)CH(2))CH(CH(3))S]](CF(3)SO(3))(4) (9) having a C(2)S(2) four-membered ring to bridge the two Ru atoms was obtained by the reaction of 1 with methylenecyclobutane, whereas the reaction with methylenecyclohexane gave [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-S(CH(2)(C=CHCH(2)CH(2)CH(2)CH(2))S)](CF(3)SO(3))(3) (10) in 69% yield via C-S bond formation and elimination of a proton. Throughout these reactions with alkenes giving a variety of products, the activation of the allylic C-H bond is always the essential and initial key step.     

Acetylide-bridged organometallic oligomers via the photochemical metathesis of methyl-iron(II) complexes

The acetylido methyl iron(II) complexes, cis/trans-[Fe(dmpe)(2)(C[triple bond]CR)(CH(3))] (1) and trans-[Fe(depe)(2)(C[triple bond]CR)(CH(3))] (2) (dmpe = 1,2-dimethylphoshinoethane; depe = 1,2-diethylphosphinoethane), were synthesized by transmetalation from the corresponding alkyl halide complexes. Acetylido methyl iron(II) complexes were also formed by transmetalation from the chloride complexes, trans-[Fe(dmpe)(2)(C[triple bond]CR)(Cl)] or trans-[Fe(depe)(2)(C[triple bond]CR)(Cl)]. The structure of trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(5))(CH(3))] (1a) was determined by single-crystal X-ray diffraction. The methyl acetylido iron complexes, [Fe(dmpe)(2)(C[triple bond]CR)(CH(3))] (1), are thermally stable in the presence of acetylenes; however, under UV irradiation, methane is lost with the formation of a metal bisacetylide. Photochemical metathesis of cis- or trans-[Fe(dmpe)(2)(CH(3))(C[triple bond]CR)] (R = C(6)H(5) (1a), 4-C(6)H(4)OCH(3) (1b)) with terminal acetylenes was used to selectively synthesize unsymmetrically substituted iron(II) bisacetylide complexes of the type trans-[Fe(dmpe)(2)(C[triple bond]CR)(C[triple bond]CR')] [R = Ph, R' = Ph (6a), 4-CH(3)OC(6)H(4) (6b), (t)()Bu (6c), Si(CH(3))(3) (6d), (CH(2))(4)C[triple bond]CH (6e); R = 4-CH(3)OC(6)H(4), R' = 4-CH(3)OC(6)H(4), (6g), (t)()Bu (6h), (CH(2))(4)C[triple bond]CH (6i), adamantyl (6j)]. The structure of the unsymmetrical iron(II) bisacetylide complex trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(5))(C[triple bond]CC(6)H(4)OCH(3))] (6b) was determined by single-crystal X-ray diffraction. The photochemical metathesis of the bis-acetylene, 1,7-octadiyne, with trans-[Fe(dmpe)(2)(CH(3))(C[triple bond]CPh)] (1a), was utilized to synthesize the bridged binuclear species trans,trans-[(C(6)H(5)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(C[triple bond]CC(6)H(5))] (11). The trinuclear species trans,trans,trans-[(C(6)H(5)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(mu-C[triple bond]C(CH(2))(4)C[triple bond]C)Fe(dmpe)(2)(C[triple bond]CC(6)H(5))] (12) was synthesized by the photochemical reaction of Fe(dmpe)(2)(C[triple bond]CPh)(C[triple bond]C(CH(2))(4)C[triple bond]CH) (6e) with Fe(dmpe)(2)(CH(3))(2). Extended irradiation of the bisacetylide complexes with phenylacetylene resulted in insertion of the terminal alkyne into one of the metal acetylide bonds to give acetylide butenyne complexes. The structure of the acetylide butenyne complex, trans-[Fe(dmpe)(2)(C[triple bond]CC(6)H(4)OCH(3))(eta(1)-C(C(6)H(5))=CH(C[triple bond]CC(6)H(4)OCH(3)))] (9a) was determined by single-crystal X-ray diffraction.     

Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands

The diastereomerically pure P-stereogenic bis(phosphinimine) ligands 4,6-(ArN[double bond, length as m-dash]PMePh)(2)dbf [Ar = 4-isopropylphenyl (Pipp): rac-4, meso-4; Ar = 2,6-diisopropylphenyl (Dipp): rac-4a; dbf = dibenzofuran] were synthesised and complexed to zinc using a protonation-alkane elimination strategy. The cationic alkylzinc complexes thus obtained, RZn[4,6-(ArN[double bond, length as m-dash]PMePh)(2)dbf][B(Ar')(4)] [Ar = Pipp, Ar' = C(6)H(3)(CF(3))(2): rac-6 (R = Et), meso-6 (R = Et), rac-7 (R = Me) meso-7 (R = Me); Ar = Dipp: rac-6a (R = Et, Ar' = C(6)H(3)(CF(3))(2)), rac-6b (R = Et, Ar' = C(6)F(5))] were investigated for their competency as initiators for the ring-opening polymerisation of rac-lactide. The formation of polylactide was achieved under relatively mild conditions (40 °C, 2-4 h) and the microstructures of the resulting polymers exhibited a slight heterotactic bias [polymer tacticity (P(r)) = 0.51-0.63].     

Reactivity at the beta-diketiminate ligand Nacnac- on titanium(IV) (Nacnac- = [Ar]NC(CH3)CHC(CH3)N[Ar], Ar = 2,6-[CH(CH3)2]2C6H3). Diimine-alkoxo and bis-anilido ligands stemming from the Nacnac- skeleton

The reaction of ketene OCCPh(2) with the four-coordinate titanium(IV) imide (L(1))Ti[double bond]NAr(OTf) (L(1)(-) = [Ar]NC(CH(3))CHC(CH(3))N[Ar], Ar = 2,6-[CH(CH(3))(2)](2)C(6)H(3)) affords the tripodal dimine-alkoxo complex (L(2))Ti[double bond]NAr(OTf) (L(2)(-) = [Ar]NC(CH(3))CHC(O)[double bond]CPh(2)C(CH(3))N[Ar]). Complex (L(2))Ti[double bond]NAr(OTf) forms from electrophilic attack of the beta-carbon of the ketene on the gamma-carbon of the Nacnac(-) NCC(gamma)CN ring. On the contrary, nucleophiles such as LiR (R(-) = Me, CH(2)(t)Bu, and CH(2)SiMe(3)) deprotonate cleanly in OEt(2) the methyl group of the beta-carbon on the former Nacnac(-) backbone to yield the etherate complex (L(3))Ti[double bond]NAr(OEt(2)), a complex that is now supported by a chelate bis-anilido ligand (L(3)(2)(-) = [Ar]NC(CH(3))CHC(CH(2))N[Ar]). In the absence of electrophiles or nucleophiles, the robust (L(1))Ti[double bond]NAr(OTf) template was found to form simple adducts with Lewis bases such as CN(t)Bu or NCCH(2)(2,4,6-Me(3)C(6)H(2)). Complexes (L(2))Ti[double bond]NAr(OTf), (L(3))Ti[double bond]NAr(OEt(2)), and the adducts (L(1))Ti[double bond]NAr(OTf)(XY) [XY = CN(t)Bu and NCCH(2)(2,4,6-Me(3)C(6)H(2))] were structurally characterized by single-crystal X-ray diffraction studies.     

Formation and chemical reactivities of a new type of double-butterfly [[Fe2(mu-CO)(CO)6]2(mu-SZS-mu)]2-: synthetic and structural studies on novel linear and macrocyclic butterfly Fe/E (E=S,Se) cluster complexes

A new type of double-butterfly [[Fe(2)(mu-CO)(CO)(6)](2)(mu-SZS-mu)](2-) (3), a dianion that has two mu-CO ligands, has been synthesized from dithiol HSZSH (Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)), [Fe(3)(CO)(12)], and Et(3)N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. For instance, while reactions of 3 with PhC(O)Cl and Ph(2)PCl give linear clusters [[Fe(2)(mu-PhCO)(CO)(6)](2)(mu-SZS-mu)] (4 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)) and [[Fe(2)(mu-Ph(2)P)(CO)(6)](2)(mu-SZS-mu)] (5 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)), reactions with CS(2) followed by treatment with monohalides RX or dihalides X-Y-X give both linear clusters [[Fe(2)(mu-RCS(2))(CO)(6)](2)(mu-SZS-mu)] (6 a-e: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2), FeCp(CO)(2)) and macrocyclic clusters [[Fe(2)(CO)(6)](2)(mu-SZS-mu)(mu-CS(2)YCS(2)-mu)] (7 a-e: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2); Y=(CH(2))(2-4), 1,3,5-Me(CH(2))(2)C(6)H(3), 1,4-(CH(2))(2)C(6)H(4)). In addition, reactions of dianions 3 with [Fe(2)(mu-S(2))(CO)(6)] followed by treatment with RX or X-Y-X give linear clusters [[[Fe(2)(CO)(6)](2)(mu-RS)(mu(4)-S)](2)(mu-SZS-mu)] (8 a-c: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2)) and macrocyclic clusters [[[Fe(2)(CO)(6)](2)(mu(4)-S)](2)(mu-SYS-mu)(mu-SZS-mu)] (9 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2); Y=(CH(2))(4)), and reactions with SeCl(2) afford macrocycles [[Fe(2)(CO)(6)](2)(mu(4)-Se)(mu-SZS-mu)] (10 d: Z=CH(2)(CH(2)OCH(2))(3)CH(2)) and [[[Fe(2)(CO)(6)](2)(mu(4)-Se)](2)(mu-SZS-mu)(2)] (11 a-d: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)). Production pathways have been suggested; these involve initial nucleophilic attacks by the Fe-centered dianions 3 at the corresponding electrophiles. All the products are new and have been characterized by combustion analysis and spectroscopy, and by X-ray diffraction techniques for 6 c, 7 d, 9 b, 10 d, and 11 c in particular. X-ray diffraction analyses revealed that the double-butterfly cluster core Fe(4)S(2)Se in 10 d is severely distorted in comparison to that in 11 c. In view of the Z chains in 10 a-c being shorter than the chain in 10 d, the double cluster core Fe(4)S(2)Se in 10 a-c would be expected to be even more severely distorted, a possible reason for why 10 a-c could not be formed.     

Dicopper(II) complexes of H-BPMP-type ligands: pH-induced changes of redox, spectroscopic ((19)F NMR studies of fluorinated complexes), structural properties, and catecholase activities

Substitution of the methyl group from the H-BPMP (HL(CH)3) ligand (2,6-bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenol) by electron withdrawing (F or CF(3)) or electron donating (OCH(3)) groups afforded a series of dinucleating ligand (HL(OCH)3, HL(F), HL(CF)3), allowing one to understand the changes in the properties of the corresponding dicopper complexes. Dinuclear Cu(II) complexes have been synthesized and characterized by spectroscopic (UV-vis, EPR, (1)H NMR) as well as electrochemical techniques and, in some cases, by single-crystal X-ray diffraction: [Cu(2)(L(OCH)3)(muOH)][(ClO(4))(2)].C(4)H(8)O, [Cu(2)(L(F))(muOH)][(ClO(4))(2)], [Cu(2)(L(F))(H(2)O)(2)][(ClO(4))(3)].C(3)D(6)O, and [Cu(2)(L(CF)3)(H(2)O)(2)][(ClO(4))(3)].4H(2)O. Significant differences are observed for the Cu-Cu distance in the two mu-hydroxo complexes (2.980 A (R = OCH(3)) and 2.967 A (R = F)) compared to the two bis aqua complexes (4.084 A (R = F) and 4.222 A (R = CF(3))). The mu-hydroxo and bis aqua complexes are reversibly interconverted upon acid/base titration. In basic medium, new species are reversibly formed and identified as the bis hydroxo complexes except for the complex from HL(CF)3 which is irreversibly transformed near pH = 10. pH-driven interconversions have been studied by UV-vis, EPR, and (1)H NMR, and the corresponding pK are determinated. In addition, with the fluorinated complexes, the changes in the coordination sphere around the copper centers and in their redox states are evidenced by the fluorine chemical shift changes ((19)F NMR). For all the complexes described here, investigations of the catechol oxidase activities (oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone) are of interest in modeling the catecholase enzyme active site and in understanding aspects of structure/reactivity. These studies show the pH-dependence for the catalytic abilities of the complexes, related with changes in the coordination sphere of the metal centers: only the mu-hydroxo complexes from HL(CH)3, HL(F), and HL(OCH)3 exhibit a catecholase activity. Modification on R-substituent induces a drastic effect on the catecholase activity: the presence of an electron donating group on the ligand increases this activity; the reverse effect is observed with an electron withdrawing group.     

Synthesis, structure, electrochemistry, and spectroelectrochemistry of hypervalent phosphorus(V) octaethylporphyrins and theoretical analysis of the nature of the PO bond in P(OEP)(CH(2)CH(3))(O)

A variety of phosphorus(V) octaethylporphyrin derivatives of the type [P(OEP)(X)(Y)](+)Z(-) (OEP: octaethylporphyrin) (X = CH(3), CH(2)CH(3), C(6)H(5), F; Y = CH(3), CH(2)CH(3), OH, OCH(3), OCH(2)CH(3), On-Pr, Oi-Pr, Osec-Bu, NHBu, NEt(2), Cl, F, O(-); Z = ClO(4), PF(6)) were prepared. X-ray crystallographic analysis of eleven compounds reveals that the degree of ruffling of the porphyrin core becomes greater and the average P-N bond distance becomes shorter as the axial ligands become more electronegative. Therefore, the electronic effect of the axial substituents plays a major role in determining the degree of ruffling although the steric effect of the substituents plays some role. A comparison of the (1)H NMR chemical shifts for the series of [P(OEP)(CH(2)CH(3))(Y)](+)Z(-) complexes with those of the corresponding arsenic porphyrins, which possess a planar core, indicates a much smaller ring current effect of the porphyrin core in the severely ruffled phosphorus porphyrins. The electrochemistry, spectroelectrochemistry and ESR spectroscopy of the singly reduced compounds are also discussed. The OH protons of [P(OEP)(X)(OH)](+) are acidic enough to generate P(OEP)(X)(O) by treatment with aq dilute NaOH. X-ray analysis of P(OEP)(CH(2)CH(3))(O) reveals that the PO bond length is very short (1.475(7) A) and is comparable to that in triphenylphosphine oxide (1.483 A). The features of the quite unique hexacoordinate hypervalent compounds are investigated by density functional calculation of a model (Por)P(CH(2)CH(3))(O) and (Por)P(F)(O) (Por: unsubstituted porphyrin).     

Reactions of a platinum(III) dimeric complex with alkynes in water: novel approach to alpha-aminoketone, alpha-iminoketone, and alpha,beta-diimine via ketonyl-Pt(III) dinuclear complexes

Reaction of the platinum(III) dimeric complex [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(NO(3))(2)](NO(3))(2) (1), prepared in situ by the oxidation of the platinum blue complex [Pt(4)(NH(3))(8)((CH(3))(3)CCONH)(4)](NO(3))(5) (2) with Na(2)S(2)O(8), with terminal alkynes CH[triple bond]CR (R = (CH(2))(n)CH(3) (n = 2-5), (CH(2))(n)CH(2)OH (n = 0-2), CH(2)OCH(3), and Ph), in water gave a series of ketonyl-Pt(III) dinuclear complexes [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(2)COR)](NO(3))(3) (3, R = (CH(2))(2)CH(3); 4, R = (CH(2))(3)CH(3); 5, R = (CH(2))(4)CH(3); 6, R = (CH(2))(5)CH(3); 7, R = CH(2)OH; 8, R = CH(2)CH(2)OH; 9, R = (CH(2))(2)CH(2)OH; 10, R = CH(2)OCH(3); 11, R = Ph). Internal alkyne 2-butyne reacted with 1 to form the complex [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(CH(3))COCH(3))](NO(3))(3) (12). These reactions show that Pt(III) reacts with alkynes to give various ketonyl complexes. Coordination of the triple bond to the Pt(III) atom at the axial position, followed by nucleophilic attack of water and hydrogen shift from the enol to keto form, would be the mechanism. The structures of complexes 3.H(2)O, 7.0.5C(3)H(4)O, 9, 10, and 12 have been confirmed by X-ray diffraction analysis. A competitive reaction between equimolar 1-pentyne and 1-pentene toward 1 produced complex 3 and [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(2)CH(OH)CH(2)CH(2)CH(3))](NO(3))(3) (14) at a molar ratio of 9:1, suggesting that alkyne is more reactive than alkene. The ketonyl-Pt(III) dinuclear complexes are susceptible to nucleophiles, such as amines, and the reactions with secondary and tertiary amines give the corresponding alpha-amino-substituted ketones and the reduced Pt(II) complex quantitatively. In the reactions with primary amines, the once formed alpha-amino-substituted ketones were further converted to the iminoketones and diimines. The nucleophilic attack at the ketonyl group of the Pt(III) complexes provides a convenient means for the preparation of alpha-aminoketones, alpha-iminoketones, and diimines from the corresponding alkynes and amines.     

Facile carbon-fluorine bond activation and subsequent functionalisation of 1,1-difluoroethylene and tetrafluoroethylene promoted by adjacent metal centres

The bridging fluoroolefin ligands in the complexes [Ir(2)(CH(3))(CO)(2)(μ-olefin)(dppm)(2)][OTf] (olefin = tetrafluoroethylene, 1,1-difluoroethylene; dppm = μ-Ph(2)PCH(2)PPh(2); OTf(-) = CF(3)SO(3)(-)) are susceptible to facile fluoride ion abstraction. Both fluoroolefin complexes react with trimethylsilyltriflate (Me(3)SiOTf) to give the corresponding fluorovinyl products by abstraction of a single fluoride ion. Although the trifluorovinyl ligand is bound to one metal, the monofluorovinyl group is bridging, bound to one metal through carbon and to the other metal through a dative bond from fluorine. Addition of two equivalents of Me(3)SiOTf to the tetrafluoroethylene-bridged species gives the difluorovinylidene-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-OTf)(μ-C=CF(2))(dppm)(2)][OTf]. The 1,1-difluoroethylene species is exceedingly reactive, reacting with water to give 2-fluoropropene and [Ir(2)(CO)(2)(μ-OH)(dppm)(2)][OTf] and with carbon monoxide to give [Ir(2)(CO)(3)(μ-κ(1):η(2)-C≡CCH(3))(dppm)(2)][OTf] together with two equivalents of HF. The trifluorovinyl product [Ir(2)(κ(1)-C(2)F(3))(OTf)(CO)(2)(μ-H)(μ-CH(2))(dppm)(2)][OTf], obtained through single C-F bond activation of the tetrafluoroethylene-bridged complex, reacts with H(2) to form trifluoroethylene, allowing the facile replacement of one fluorine in C(2)F(4) with hydrogen.     

Reactions of halofluorocarbons with group 6 complexes M(C(5)H(5))(2)L (M = Mo, W; L = C(2)H(4), CO). Fluoroalkylation at molybdenum and tungsten, and at cyclopentadienyl or ethylene ligands.

The molybdenum(II) and tungsten(II) complexes [MCp(2)L] (Cp = eta(5)-cyclopentadienyl; L = C(2)H(4), CO) react with perfluoroalkyl iodides to give a variety of products. The Mo(II) complex [MoCp(2)(C(2)H(4))] reacts with perfluoro-n-butyl iodide or perfluorobenzyl iodide with loss of ethylene to give the first examples of fluoroalkyl complexes of Mo(IV), MoCp(2)(CF(2)CF(2)CF(2)CF(3))I (8) and MoCp(2)(CF(2)C(6)F(5))I (9), one of which (8) has been crystallographically characterized. In contrast, the CO analogue [MoCp(2)(CO)] reacts with perfluorobenzyl iodide without loss of CO to give the crystallographically characterized salt, [MoCp(2)(CF(2)C(6)F(5))(CO)](+)I(-) (10), and the W(II) ethylene precursor [WCp(2)(C(2)H(4))] reacts with perfluorobenzyl iodide without loss of ethylene to afford the salt [WCp(2)(CF(2)C(6)F(5))(C(2)H(4))](+)I(-) (11). These observations demonstrate that the metal-carbon bond is formed first. In further contrast the tungsten precursor [WCp(2)(C(2)H(4))] reacts with perfluoro-n-butyl iodide, perfluoro-iso-propyl iodide, and pentafluorophenyl iodide to give fluoroalkyl- and fluorophenyl-substituted cyclopentadienyl complexes WCp(eta(5)-C(5)H(4)R(F))(H)I (12, R(F) = CF(2)CF(2)CF(2)CF(3); 15, R(F) = CF(CF(3))(2); 16, R(F) = C(6)F(5)); the Mo analogue MoCp(eta(5)-C(5)H(4)R(F))(H)I (14, R(F) = CF(CF(3))(2)) is obtained in similar fashion. The tungsten(IV) hydrido compounds react with iodoform to afford the corresponding diiodides WCp(eta(5)-C(5)H(4)R(F))I(2) (13, R(F) = CF(2)CF(2)CF(2)CF(3); 18, R(F) = CF(CF(3))(2); 19, R(F) = C(6)F(5)), two of which (13 and 19) have been crystallographically characterized. The carbonyl precursors [MCp(2)(CO)] each react with perfluoro-iso-propyl iodide without loss of CO, to afford the exo-fluoroalkylated cyclopentadiene M(II) complexes MCp(eta(4)-C(5)H(5)R(F))(CO)I (21, M = Mo; 22, M = W); the exo-stereochemistry for the fluoroalkyl group is confirmed by an X-ray structural study of 22. The ethylene analogues [MCp(2)(C(2)H(4))] react with perfluoro-tert-butyl iodide to yield the products MCp(2)[(CH(2)CH(2)C(CF(3))(3)]I (25, M = Mo; 26, M = W) resulting from fluoroalkylation at the ethylene ligand. Attempts to provide positive evidence for fluoroalkyl radicals as intermediates in reactions of primary and benzylic substrates were unsuccessful, but trapping experiments with CH(3)OD (to give R(F)D, not R(F)H) indicate that fluoroalkyl anions are the intermediates responsible for ring and ethylene fluoroalkylation in the reactions of secondary and tertiary fluoroalkyl substrates.     

On the use of mixtures of organotin species for catalytic enantioselective ketone allylation--a detective story

In the presence of enantiopure MTBH(2)(monothiobinaphthol, 2-hydroxy-2[prime or minute]mercapto-1,1[prime or minute]-binaphthyl; 0.2 eq.) quantitative allylation of ArC([double bond]O)Me takes place with impure Sn(CH(2)CH[double bond]CH(2))(4)(prepared from allyl chloride, air-oxidised magnesium and SnCl(4)) to yield tert-homoallylic alcohols in 85-92% ee. In the same process highly purified, or commercial, Sn(CH(2)CH[double bond]CH(2))(4) yields material of only 35-50% ee. The origin of these effects is the presence of small amounts of the compounds, EtSn(CH(2)CH[double bond]CH(2))(3), ClSn(CH(2)CH[double bond]CH(2))(3) ClSnEt(CH(2)CH[double bond]CH(2))(2) in the tetraallyltin sample and the presence of traces of water (which inhibits achiral background reactions). All the triallyl and diallyl species enhance the stereoselectivity in the catalytic allylation reaction, the chlorides more so than the ethyl compound. Hydrolysis of ClSnEt(CH(2)CH[double bond]CH(2))(2) affords crystallographically characterised Sn(4)(mu(3)-O)(mu(2)-Cl)(2)Cl(2)Et(4)(CH(2)CH[double bond]CH(2))(4). Reaction of this latter compound with MTBH(2) leads to the most potent catalyst.     

Conformational analysis and assignments of relative stereocenter configurations in fluoroalkyl-iridium complexes using 19F[1H] HOESY experiments. Comparison with solid-state X-ray structural results

Solution conformations about the metal-carbon bond of the secondary fluoroalkyl ligands in iridium complexes [IrCp(PMe(3))(R(F))X] [Cp* = C(5)Me(5); R(F) = CF(CF(3))(2), X = I (1), CH(3) (2); R(F) = CF(CF(3))(CF(2)CF(3)), X = I (4), CH(3) (5)] have been determined using (19)F[(1)H] HOESY techniques. The molecules adopt the staggered conformation with the tertiary fluorine in the more hindered sector between the PMe(3) and X ligands, with CF(3) (and CF(2)CF(3)) substituents lying in the less hindered regions between PMe(3) and Cp or X and Cp. In molecules containing the CF(CF(3))(2) ligand, these conformations are identical to those adopted in the solid state. For compound 4, containing the CF(CF(3))(CF(2)CF(3)) ligand, two diastereomers are observed in solution. Solution conformations and relative stereocenter configuration assignments have been obtained using (19)F[(1)H] HOESY and correlated with the X-ray structure for the major diastereomer of 4, which has the (S(Ir), S(C)) or (R(Ir), R(C)) configuration. Relative stereocenter configurations of analogue 5, for which no suitable crystals could be obtained, were assigned using (19)F[(1)H] HOESY and proved to be different from 4, with 5 preferring the (S(Ir), R(C)) or (R(Ir), S(C)) configuration.     

Synthesis and reactivity of cationic niobium and tantalum methyl complexes supported by imido and β-diketiminato ligands

The synthesis and reactivity of the cationic niobium and tantalum monomethyl complexes [(BDI)MeM(N(t)Bu)][X] (BDI = [Ar]NC(CH(3))CHC(CH(3))N[Ar], Ar = 2,6-(i)Pr(2)C(6)H(3); M = Nb, Ta; X = MeB(C(6)F(5))(3), B(C(6)F(5))(4)] was investigated. The cationic alkyl complexes failed to irreversibly bind CO but formed phosphine-trapped acyl complexes [(BDI)(R(3)PC(O)Me)M(N(t)Bu)][B(C(6)F(5))(4)] (R = Et, Cy) in the presence of a combination of trialkylphosphines and CO. Treatment of the monoalkyl cationic Nb complex with XylNC (Xyl = 2,6-Me(2)-C(6)H(3)) resulted in irreversible formation of the iminoacyl complex [(BDI)(XylN[double bond, length as m-dash]C(Me))Nb(N(t)Bu)][B(C(6)F(5))(4)], which did not bind phosphines but would add a methide group to the iminoacyl carbon to provide the known ketimine complex (BDI)(XylNCMe(2))Nb(N(t)Bu). Further stoichiometric chemistry explored i) migratory insertion reactions to form new alkoxide, amidinate, and ketimide complexes; ii) protonolysis reactions with Ph(3)SiOH to form thermally robust cationic siloxide complexes; and iii) catalytic high-density polyethylene formation mediated by the cationic Nb methyl complex.     

Intramolecular C-N bond formation reactions catalyzed by ruthenium porphyrins: amidation of sulfamate esters and aziridination of unsaturated sulfonamides

Ruthenium porphyrins [Ru(F(20)-TPP)(CO)] (F(20)-TPP = 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) and [Ru(Por*)(CO)] (Por = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters p-X-C(6)H(4)(CH(2))(2)OSO(2)NH(2) (X = Cl, Me, MeO), XC(6)H(4)(CH(2))(3)OSO(2)NH(2) (X = p-F, p-MeO, m-MeO), and Ar(CH(2))(2)OSO(2)NH(2) (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI(OAc)(2) to afford the corresponding cyclic sulfamidates in up to 89% yield with up to 100% substrate conversion; up to 88% ee was attained in the asymmetric intramolecular amidation catalyzed by [Ru(Por)(CO)]. Reaction of [Ru(F(20)-TPP)(CO)] with PhI[double bond]NSO(2)OCH(2)CCl(3) (prepared by treating the sulfamate ester Cl(3)CCH(2)OSO(2)NH(2) with PhI(OAc)(2)) afforded a bis(imido)ruthenium(VI) porphyrin, [Ru(VI)(F(20)-TPP)(NSO(2)OCH(2)CCl(3))(2)], in 60% yield. A mechanism involving reactive imido ruthenium porphyrin intermediate was proposed for the ruthenium porphyrin-catalyzed intramolecular amidation of sulfamate esters. Complex [Ru(F(20)-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI(OAc)(2), producing corresponding bicyclic aziridines in up to 87% yield with up to 100% substrate conversion and high turnover (up to 2014).     

Chiral fluorous dialkoxy-diamino zirconium complexes: synthesis and use in stereospecific polymerization of 1-hexene

New catalysts for the isospecific polymerization of 1-hexene based on cationic zirconium complexes incorporating the tetradentate fluorous dialkoxy-diamino ligands [OC(CF(3))(2)CH(2)N(Me)(CH(2))(2)N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(2)NO)(2-)] and [OC(CF(3))(2)CH(2)N(Me)(1R,2R-C(6)H(10))N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(Cy)NO)(2-)] have been developed. The chiral fluorous diamino-diol [(ON(Cy)NO)H(2), 2] was prepared by ring-opening of the fluorinated oxirane (CF(3))(2)COCH(2) with (R,R)-N,N'-dimethyl-1,2-cyclohexanediamine. Proligand 2 reacts cleanly with [Zr(CH(2)Ph)(4)] and [Ti(OiPr)(4)] precursors to give the corresponding dialkoxy complexes [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3) and [Ti(OiPr)(2)(ON(Cy)NO)] (4), respectively. An X-ray diffraction study revealed that 3 crystallizes as a 1:1 mixture of two diastereomers (Lambda-3 and Delta-3), both of which adopt a distorted octahedral structure with trans-O, cis-N, and cis-CH(2)Ph ligands. The two diastereomers Lambda-3 and Delta-3 adopt a C(2)-symmetric structure in toluene solution, as established by NMR spectroscopy. Cationic complexes [Zr(CH(2)Ph)(ON(2)NO)(THF)(n)](+) (n=0, anion=[B(C(6)F(5))(4)](-), 5; n=1, anion=[PhCH(2)B(C(6)F(5))(3)](-), 6) and [Zr(CH(2)Ph)(ON(Cy)NO)(THF)](+)[PhCH(2)B(C(6)F(5))(3)](-) (7) were generated from the neutral parent precursors [Zr(CH(2)Ph)(2)(ON(2)NO)] (H) and [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3), and their possible structures were determined on the basis of (1)H, (19)F, and (13)C NMR spectroscopy and DFT methods. The neutral zirconium complexes H and 3 (Lambda-3/Delta-3 mixture), when activated with B(C(6)F(5))(3) or [Ph(3)C](+)[B(C(6)F(5))(4)](-), catalyze the polymerization of 1-hexene with overall activities of up to 4500 kg PH mol Zr(-1) h(-1), to yield isotactic-enriched (up to 74 % mmmm) polymers with low-to-moderate molecular weights (M(w)=4800-47 200) and monodisperse molecular-weight distributions (M(w)/M(n)=1.17-1.79).     

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C(5)R'(4)(CH(2))(2)PR(2)] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C(5)R'(4)(C(2)H(4)) with LiPR(2). C(5)Et(4)HSiMe(2)CH(2)PMe(2), was prepared from reaction of Li[C(5)Et(4)] with Me(2)SiCl(2) followed by Me(2)PCH(2)Li. The lithium salts were reacted with [RhCl(CO)(2)](2), [IrCl(CO)(3)] or [Co(2)(CO)(8)] to give [M(C(5)R'(4)(CH(2))(2)PR(2))(CO)] (M = Rh, R = Et, R' = H or Me, R = Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (Cp' = C(5)Me(4)), the most electron rich of the complexes. [Rh(C(5)Et(4)SiMe(2)CH(2)PMe(2))(CO)] may be a dimer. [Co(2)(CO)(8)] reacts with C(5)H(5)(CH(2))(2)PEt(2) or C(5)Et(4)HSiMe(2)CH(2)PMe(2) (L) to give binuclear complexes of the form [Co(2)(CO)(6)L(2)] with almost linear PCoCoP skeletons. [Rh(Cp'(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH(2))(2)PPh(2))(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI(2)(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt(3))(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH(2))(2)PEt(2))I(2)], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH(2))(2)PEt(2))(CO)]. Neither of [M(Cp'(CH(2))(2)PEt(2))(CO)] (M = Co or Ir) was active for methanol carbonylation under these conditions, nor under many other conditions investigated, except that [Ir(Cp'(CH(2))(2)PEt(2))(CO)] showed some activity at higher temperature (190 degrees C), probably as a result of degradation to [IrI(2)(CO)(2)](-). [M(Cp'(CH(2))(2)PEt(2))(CO)] react with MeI to give [M(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] (M = Co or Rh) or [Ir(Cp'(CH(2))(2)PEt(2))Me(CO)]I. The rates of oxidative addition of MeI to [Rh(C(5)H(4)(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are 62 and 1770 times faster than to [Cp*Rh(CO)(2)]. Methyl migration is slower, however. High pressure NMR studies show that [Co(Cp'(CH(2))(2)PEt(2))(CO)] and [Cp*Rh(PEt(3))(CO)] are unstable towards phosphine oxidation and/or quaternisation under methanol carbonylation conditions, but that [Rh(Cp'(CH(2))(2)PEt(2))(CO)] does not exhibit phosphine degradation, eventually producing inactive [Rh(Cp'(CH(2))(2)PEt(2))I(2)] at least under conditions of poor gas mixing. The observation of [Rh(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] under methanol carbonylation conditions suggests that the rhodium centre has become so electron rich that reductive elimination of ethanoyl iodide has become rate determining for methanol carbonylation. In addition to the high electron density at rhodium.     

Regioselective Substitution Reactions of Sulfur(VI)-Nitrogen-Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl(2))(2)] (X = Cl or F) with Oxygen-Based Nucleophiles

The reactions of the cyclic thionylphosphazenes [NSOX(NPCl(2))(2)] (1, X = Cl; 2, X = F) with three oxygen-based nucleophiles of increasing basicity, sodium phenoxide (NaOPh), sodium trifluoroethoxide (NaOCH(2)CF(3)), and sodium butoxide (NaOBu) have been studied. The reaction of 1 and 2 with 4 equiv of NaOPh at 25 degrees C yielded the regioselectively tetrasubstituted species [NSOX{NP(OPh)(2)}(2)] (5d, X = Cl; 6d, X = F). Further reaction of 5d with an additional 2 equiv of NaOPh over several days or at elevated temperatures gave the fully substituted compound [NSO(OPh){NP(OPh)(2)}(2)] (5e), whereas 6d did not react further. The reaction of 1 and 2 with 5 equiv of NaOCH(2)CF(3) yielded in both cases [NSO(OCH(2)CF(3)){NP(OCH(2)CF(3))(2)}(2)] (7e), and similarly reaction with 5 equiv of NaOBu yielded [NSO(OBu){NP(OBu)(2)}(2)] (9e). In all cases, the reactions were monitored by (31)P NMR and (where applicable) (19)F NMR and were found to involve complete substitution at phosphorus via a predominantly vicinal pathway, followed by substitution at sulfur. Substitutional control of the reactions of NaOPh, NaOBu, with 1 and 2 was found to conform to the following general order of reactivity, PCl(2) > PCl(OR) > SOX (X = Cl, F). Although the reaction with NaOCH(2)CF(3) followed the same order of reactivity, a significant enhancement of reaction rate was detected with each equivalent of trifluoroethoxide added. Reaction of 7e with excess NaOCH(2)CF(3) led to elimination of (CF(3)CH(2))(2)O and the formation of the salts Na[NSO(OCH(2)CF(3))NP(OCH(2)CF(3))(2)NP(OCH(2)CF(3))O] (11) and Na[NS(O)O{NP(OCH(2)CF(3))(2)}(2)] (12). Crystals of 6d are triclinic, space group P&onemacr;, with a = 9.789(3) ?, b = 11.393(4) ?, c = 12.079(5) ?, alpha = 107.40(3) degrees, beta = 91.23(3) degrees, gamma = 93.18(3), V = 1283.6(8) ?(3), and Z = 2. Crystals of 5e are monoclinic, space group C2/c, with a = 32.457(3) ?, b = 10.747(1) ?, c = 18.294(2) ?, beta = 110.37(1) degrees, V = 5982.4(9) ?(3), and Z = 8.