Cyclic and linear polyferrocenes with silicon and tin as alternating bridges

The synthesis and characterization of ferrocene-based oligomers that contained two different elements (Si and Sn) as alternating bridges is described for the first time. The salt-metathesis reaction of R(2) Si[(C(5) H(4) )Fe(C(5) H(4) Li)](2) (R=Me, Et) with R'(2) SnCl(2) (R'=Me, nBu, tBu) afforded a mixture of oligomers (6(Me) SnMe(2), 6(Et) SnMe(2), 6(Me) SnnBu(2), 6(Et) SnnBu(2), 6(Me) SntBu(2), and 6(Et) SntBu(2)). These oligomers were characterized by (1) H, (13) C, (29) Si, and (119) Sn?NMR spectroscopy and by mass spectrometry. MS (MALDI-TOF) studies of 6(Et) SnMe(2) revealed the presence of linear (l) and cyclic (c) species that contained up to 20?ferrocene moieties. The molecular weights of the polymers were determined by gel-permeation chromatography (GPC) and by dynamic-light scattering (DLS). GPC analysis revealed average molecular weights of 2100-6300?Da with respect to polystyrene as a standard. DLS analysis yielded very similar results. Some compounds, c-(6(Me) SnMe(2) )(1), c-(6(Me) SntBu(2))(2), c-(6(Et) SnMe(2))(1), c-(6(Et) SntBu(2))(2), l-(6(Me) SnnBu(2) )(2), and l-(6(Me) SnnBu(2))(3), which contained up to six ferrocene moieties, were isolated in their pure form either by column chromatography or by crystallization. The Si- and Sn-bridged macrocycles that contained four ferrocene units (c-(6(Me) SntBu(2))(2) and c-(6(Et) SntBu(2))(2)) were structurally characterized by single-crystal X-ray analysis.     

Osmabenzenes from the reactions of a dicationic osmabenzyne complex

Treatment of the osmabenzyne Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)Cl(2)(PPh(3))(2) (1) with 2,2'-bipyridine (bipy) and thallium triflate (TlOTf) produces the thermally stable dicationic osmabenzyne [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) (2). The dicationic osmabenzyne 2 reacts with ROH (R = H, Me) to give osmabenzene complexes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf, in which the metallabenzene ring deviates significantly from planarity. In contrast, reaction of the dicationic complex 2 with NaBH(4) produces a cyclopentadienyl complex, presumably through the osmabenzene intermediate [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf. The higher thermal stability of [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf relative to [Os(=CHC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf can be related to the stabilization effect of the OR groups on the metallacycle. A theoretical study shows that conversion of the dicationic osmabenzyne complex [Os([triple bond]CC(SiMe(3))=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)](OTf)(2) to a carbene complex by reductive elimination is thermodynamically unfavorable. The theoretical study also suggests that the nonplanarity of the osmabenzenes [Os(=C(OR)CH=C(Me)C(SiMe(3))=CH)(bipy)(PPh(3))(2)]OTf is mainly due to electronic reasons.     

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.     

Synthesis of Pd3Tl and Pd6Tl2 complexes based on a trinuclear aryl-palladium(II) complex acting as a metallaligand toward thallium(I) through Tl-arene and Tl-I bonds

The metallaligand [(PdIL(2))(3)(C(6)Me(3)-1,3,5)] (L(2) = 4,4'-di-tert-butyl-2-2'-bipyridine = tbbpy) reacts with TlOTf to afford the complex [{(PdIL(2))(3)C(6)Me(3)-1,3,5}Tl]OTf, which exists in the solid state as a 2:1 mixture of monomer and dimer, both showing Tl(I)-I and Tl(I)-η(6)-mesitylene bonds. In solution, only the monomer is observed. Heating of toluene solutions of [(PdIL(2))(3)(C(6)Me(3)-1,3,5)] affords the dinuclear complex [(PdIL(2))(2)(C(6)HMe(3)-1,3,5)].     

Electrophilic attack on trinuclear titanium imido-nitrido systems

Alkylation of [{Ti(η(5)-C(5)Me(5))(μ-NH)}(3)(μ(3)-N)] with MeOTf occurs at the imido ligands to produce the methylamido derivative [Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)(μ-NH)(2)(μ-NHMe)(OTf)] which readily rearranges to form the methylimido complex [Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)(μ-NH)(μ-NH(2))(μ-NMe)(OTf)].     

New group 11 complexes with metal-selenium bonds of methyldiphenylphosphane selenide: a solid state, solution and theoretical investigation

Reactions between methyldiphenylphosphane selenide, SePPh(2)Me, and different group 11 metal starting materials {CuCl, [CuNO(3)(PPh(3))(2)], AgOTf, [AgOTf(PPh(3))] (OTf = OSO(2)CF(3)), [AuCl(tht)], [Au(C(6)F(5))(tht)] and [Au(C(6)F(5))(3)(tht)] (tht = tetrahydrothiophene)} were performed in order to obtain several new species with metal-selenium bonds. The new complexes [CuCl(SePPh(2)Me)] (1), [AgOTf(SePPh(2)Me)] (2), [AuCl(SePPh(2)Me)] (5), [Au(C(6)F(5))(SePPh(2)Me)] (6) and [Au(C(6)F(5))(3)(SePPh(2)Me)] (7) were isolated and structurally characterized in solution by multinuclear NMR spectroscopy ((1)H, (31)P, (77)Se and (19)F where appropriate). Solid products were isolated also from the reactions between SePPh(2)Me and [CuNO(3)(PPh(3))(2)] or [AgOTf(PPh(3))], respectively. NMR experiments, including low temperature (1)H and (31)P NMR, revealed for them a dynamic behaviour in solution, involving the transfer of selenium from PPh(2)Me to PPh(3). In case of the isolated silver(i) containing solid an equilibrium between, respectively, monomeric [AgOTf(PPh(3))(SePPh(2)Me)] (3) and [AgOTf(PPh(2)Me)(SePPh(3))] (4), and dimeric [Ag(PPh(3))(μ-SePPh(2)Me)](2)(OTf)(2) (3a) and [Ag(PPh(2)Me)(μ-SePPh(3))](2)(OTf)(2) (4a) species was observed in solution. In case of the isolated copper(i) containing solid the NMR studies brought no clear evidence for a similar behaviour, but it can not be excluded in a first stage of the reaction. However the transfer of selenium between the two triorganophosphanes takes place also in this case, but the NMR spectra suggest that the final reaction mixture contains the free triorganophospane selenides SePPh(2)Me and SePPh(3) as well as the complex species [CuNO(3)(PPh(3))(2)], [CuNO(3)(PPh(2)Me)(2)] and [CuNO(3)(PPh(3))(PPh(2)Me)] in equilibrium. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) 6 and gold(III) 7 complexes. In case of compound 6 weak aurophilic gold(I)···gold(I) contacts were also observed in the crystal. DFT calculations were performed in order to understand the solution behaviour of the silver(I) and copper(I) species containing both P(III) and P(V) ligands, to verify the stability of possible dimeric species and to account for the aurophilic interactions found for 6. In addition, the nature of the electronic transitions involved in the absorption/emission processes observed for 6 and 7 in the solid state were also investigated by means of TD-DFT calculations.     

Electronic and medium effects on the rate of arene C [bond] H activation by cationic Ir(III) complexes

A detailed mechanistic study of arene C [bond] H activation in CH(2)Cl(2) solution by Cp(L)IrMe(X) [L = PMe(3), P(OMe)(3); X = OTf, (CH(2)Cl(2))BAr(f); (BAr(f) = B[3,5-C(6)H(3)(CF(3))(2)](4))(-)] is presented. It was determined that triflate dissociation in Cp(L)IrMe(OTf), to generate tight and/or solvent-separated ion pairs containing a cationic iridium complex, precedes C [bond] H activation. Consistent with the ion-pair hypothesis, the rate of arene activation by Cp(L)IrMe(OTf) is unaffected by added external triflate salts, but the rate is strongly dependent upon the medium. Thus the reactivity of Cp(PMe(3))IrMe(OTf) can be increased by almost 3 orders of magnitude by addition of (n-Hex)(4)NBAr(f), presumably because the added BAr(f) anion exchanges with the OTf anion in the initially formed ion pair, transiently forming a cation/borate ion pair in solution (special salt effect). In contrast, addition of (n-Hex)(4)NBAr(f) to [CpPMe(3)Ir(Me)CH(2)Cl(2)][BAr(f)] does not affect the rate of benzene activation; here there is no initial covalent/ionic pre-equilibrium that can be perturbed with added (n-Hex)(4)NBAr(f). An analysis of the reaction between Cp(PMe(3))IrMe(OTf) and various substituted arenes demonstrated that electron-donating substituents on the arene increase the rate of the C [bond] H activation reaction. The rate of C(6)H(6) activation by [Cp(PMe(3))Ir(Me)CH(2)Cl(2)][BAr(f)] is substantially faster than [Cp(P(OMe)(3))Ir(Me)CH(2)Cl(2)][BAr(f)]. Density functional theory computations suggest that this is due to a less favorable pre-equilibrium for dissociation of the dichloromethane ligand in the trimethyl phosphite complex, rather than to a large electronic effect on the C [bond] H oxidative addition transition state. Because of these combined effects, the overall rate of arene activation is increased by electron-donating substituents on both the substrate and the iridium complex.     

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.     

Azido- or hydroxyl-capped half-cubanes containing Cp*Rh fragments: [Cp*3Rh3(mu-X)3(mu3-X)]2+ (X-=OH- or N3-)

Treatment of [Cp*Rh(H(2)O)(3)](OTf)(2) (1) with Me(3)SiNH-t-Bu in acetone gave a hydroxyl-capped half-cubane [Cp*(3)Rh(3)(mu-OH)(3)(mu(3)-OH)](OTf)(3)(t-BuNH(3)) (2). Slow diffusion of Me(3)SiN(3) in diethyl ether into compound in acetone produced an azido-capped half-cubane [Cp*(3)Rh(3)(mu-N(3))(3)(mu(3)-N(3))](OTf)(2) (3). On the other hand, treating 1 with Me(3)SiN(3) in acetone gave an azido-bridged, dinuclear rhodium(III) complex [Cp*Rh(mu-N(3))(OH(2))](2)(OTf)(2) (4). Complexes 2 and 3 represent the first azido- or hydroxyl-capped, incomplete cubane-type Rh clusters. Under appropriate conditions, complexes 2 and 3 could be converted to complex 4. The structures of all products were determined by X-ray diffraction.     

The bridged binding mode as a new, versatile template for the selective activation of carbon-fluorine bonds in fluoroolefins: activation of trifluoroethylene

We report the selective activation of carbon-fluorine bonds in trifluoroethylene using the diiridium complex [Ir(2)(CH(3))(CO)(2)(dppm)(2)][OTf] (1). Coordination of trifluoroethylene in a bridging position between the two metals in 1 results in facile fluoride ion loss in three different ways. Attack by strong fluorophiles such as Me(3)SiOTf and HOTf results in F(-) removal from one of the geminal fluorines to give the cis-difluorovinyl-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-κ(1):η(2)-C(F)═CFH)(dppm)(2)][OTf]. A second activation can also be accomplished by addition of excess Me(3)SiOTf to give the fluorovinylidene-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-C(2)FH)(dppm)(2)][OTf](2). Interestingly, activation of the trifluoroethylene-bridged precursor by water also occurs, yielding [Ir(2)(CH(3))(CO)(2)(κ(1)-C(H)═CF(2))(μ-OH)(dppm)(2)][OTf], in which the lone vicinal fluorine is removed, leaving a geminal arrangement of fluorines in the product. A [1,2]-fluoride shift can also be induced in the trifluoroethylene-bridged precursor upon the addition of CO to give the 2,2,2-trifluoroethylidene-bridged product [Ir(2)(CH(3))(CO)(3)(μ-C(H)CF(3))(dppm)(2)][CF(3)SO(3)]. Addition of hydrogen to the cis-difluorovinyl-bridged product results in the quantitative elimination of cis-difluoroethylene, while its reaction with CO yields a mixture of cis-difluoropropene and 2,3-difluoropropene by reductive elimination of the methyl and difluorovinyl groups with an accompanying isomerization in the case of the second product. Finally, protonation of the 2,2,2-trifluoroethylidene-bridged product liberates 1,1,1-trifluoroethane, in which one hydrogen (H(+)) is from the acid while the other hydrogen (H(-)) is derived from activation of the methyl group.     

Synthesis of functionalized diaryldimethylstannanes from the Me2Sn2- dianion by SRN1 reactions

[reaction: see text] The reaction of different ArCl with the Me(2)Sn(2)(-) dianion in liquid ammonia under irradiation afforded Ar(2)SnMe(2) in good yields (68-85%). The results obtained clearly indicate that the reaction proceeded through an S(RN)1 reaction. As a synthetic application of these Ar(2)SnMe(2), the homocoupling is described in the presence of Cu(NO(3))(2).2.5H(2)O to afford the biaryls. These reactions proceeded almost quantitatively.     

NMR studies on the novel heterobimetallic complexes [M(dppm)(Ph(2)PCH(2)PPh(2)PPPP) {Pt(PPh3)2}]OTf (M = Rh, Ir) derived from the stepwise activation of white phosphorus

The solution structures of the novel heterobimetallic complexes [Ir(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))2}]OTf and [Rh(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))(2)}]OTf derived from the reaction of Rh and Ir--P(5) precursors with [Pt(C2H4)(PPh3)2] have been unambiguously assigned on the basis of 1H NMR and 31P{1H} NMR data. The results are in agreement with the regio-selective insertion of the {Pt(PPh3)2} moiety resulting in a new pentaphosphorus topology which agrees with the formal formation of a unique phosphonium(+)-tetraphosphabutadienide(2-) ligand.     

Synthesis and reactivity of the hydrido- and alkylrhenium methylidene complexes Cp*(PMe3)2(R)Re=CH2 (R = H, CH3)

Protonolysis of the dimethylrhenium(III) compound Cp(PMe(3))(2)Re(CH(3))(2) (3) led to formation of the highly reactive hydridorhenium methylidene compound [Cp(PMe(3))(2)Re(CH(2))(H)][OTf] (4), which was characterized spectroscopically at low temperature. Although 4 decomposed above -30 degrees C, reactivity studies performed at low temperature indicated it was in equilibrium with the coordinatively unsaturated methylrhenium complex [Cp(PMe(3))(2)Re(CH(3))][OTf] (2). Methylidene complex 4 was found to react with PMe(3) to afford [Cp(PMe(3))(3)Re(CH(3))][OTf] (6) and with chloride anion to give Cp(PMe(3))(2)Re(Me)Cl (7). When BAr(f) anion was added to 4, the thermally stable methylrhenium methylidene complex [Cp(PMe(3))(2)Re(CH(2))(CH(3))][BAr(f)] (8) was isolated upon warming to room temperature. The mechanisms of formation of both 4 and 8 are discussed in detail, including DFT calculations. The novel carbonyl ligated complex Cp(CO)(2)Re(CH(3))OTf (12) was prepared, isolated, and found to not undergo migration reactions to form methylidene complexes.     

Direct detection of dimethylstannylene and tetramethyldistannene in solution and the gas phase by laser flash photolysis of 1,1-dimethylstannacyclopent-3-enes

The photochemistry of 1,1-dimethyl- and 1,1,3,4-tetramethylstannacyclopent-3-ene (4a and 4b, respectively) has been studied in the gas phase and in hexane solution by steady-state and 193-nm laser flash photolysis methods. Photolysis of the two compounds results in the formation of 1,3-butadiene (from 4a) and 2,3-dimethyl-1,3-butadiene (from 4b) as the major products, suggesting that cycloreversion to yield dimethylstannylene (SnMe2) is the main photodecomposition pathway of these molecules. Indeed, the stannylene has been trapped as the Sn-H insertion product upon photolysis of 4a in hexane containing trimethylstannane. Flash photolysis of 4a in the gas phase affords a transient absorbing in the 450-520-nm range that is assigned to SnMe2 by comparison of its spectrum and reactivity to those previously reported from other precursors. Flash photolysis of 4b in hexane solution affords results consistent with the initial formation of SnMe2 (lambda(max) approximately 500 nm), which decays over approximately 10 micros to form tetramethyldistannene (5b; lambda(max) approximately 470 nm). The distannene decays over the next ca. 50 micros to form at least two other longer-lived species, which are assigned to higher SnMe2 oligomers. Time-dependent DFT calculations support the spectral assignments for SnMe2 and Sn2Me4, and calculations examining the variation in bond dissociation energy with substituent (H, Me, and Ph) in disilenes, digermenes, and distannenes rule out the possibility that dimerization of SnMe2 proceeds reversibly. Addition of methanol leads to reversible reaction with SnMe2 to form a transient absorbing at lambda(max) approximately 360 nm, which is assigned to the Lewis acid-base complex between SnMe2 and the alcohol.     

Interconversion between the enantiomers of chiral five-coordinate Me3Pt(IV) complexes

The dinuclear Me(2)Pt(II) complexes of 3,4-bis(quinolin-8-yl)thiophene (1a), 3,4-bis(6 trifluoromethoxyquinolin-8-yl)thiophene (1b), and 3,4-bis(2-methylquinolin-8-yl)thiophene (1c) react with MeOTf (OTf = trifluoromethanesulfonate) to afford the corresponding chiral mononuclear five-coordinate Me(3)Pt(IV) complexes [PtMe(3)(1a)]OTf (3a), [PtMe(3)(1b)]OTf (3b), and [PtMe(3)(1c)]OTf (3c), respectively. [PtMe(3)(1c)]BAr(F)(4) (3d) (where BAr(F)(4) = [B{C(6)H(3)-3,5-(CF(3))(2)}(4)]) has also been synthesized for structural study. While 3a appears to be symmetric in solution and asymmetric in solid state, 3c and 3d are asymmetric in both solution and solid state. The chirality originates from interligand repulsion, rather than any unsymmetrical ligand. Variable-temperature NMR and computational studies suggest a ligand-twisting isomerization pathway for the interconversion of the enantiomers, rather than the rotational exchange of three CH(3) ligands on the metal center.     

Binding cooperativity of two different Lewis acid groups at the edge of ferrocene

The binding properties of heteronuclear bidentate Lewis acids, in which an organoboron and an organotin moiety are attached adjacent to each other at one of the Cp rings of ferrocene, have been studied. Treatment of [1,2-fc(SnMe2Cl)(BClMe)] (1-Cl) (fc = ferrocenediyl) with one equivalent of pyridine or 4-dimethylaminopyridine (DMAP) resulted in diastereoselective complexation of boron. Adducts 2 and 3 have been studied by multinuclear NMR, and the stereoselectivity of complexation was further confirmed by single crystal X-ray diffraction of 2. The importance of cooperative effects that involve an intramolecular B-ClSn interaction on the diastereoselectivity is evident from comparison with binding studies on the phenyl-substituted analogue [1,2-fc(SnMe2Cl)(BPhMe)] (1-Ph). Complexation of 1-Ph led to diastereomeric mixtures of adducts 4 and 5, respectively, which were identified by multinuclear NMR including NOESY experiments. The solid-state structure of one of the diastereomers of 5 was confirmed by X-ray crystallography. Facile isomerization was found in solution and the barrier of activation was determined by VT NMR studies (4: Delta(#)(298) = 54.9+/-0.4 kJ mol(-1); 5: Delta(#)(298) = 70.3+/-0.1 kJ mol(-1)). Competitive binding of pyridine to 1-Cl and [FcB(Cl)Me] (Fc = ferrocenyl) showed that cooperative effects between tin and boron lead to significant Lewis acidity enhancement. Binding of a second nucleophile in the presence of excess of base occurred also at boron. The novel zwitterionic complexes [1,2-fc(BMe(py)2)(SnMe2Cl2)] (6) and [1,2-fc(BMe(dmap)(2))(SnMe(2)Cl2)] (7) formed, which consist of boronium cation and stannate anion moieties. The structure of 7 in the solid-state was confirmed by X-ray crystallography. Multinuclear NMR data and competition experiments indicate weak binding of chloride to tin in 7 and partial dissociation in solution.     

Monocyclic di- and triphosphinophosphonium cations: new foundational frameworks for catena-phosphorus chemistry

The synthesis and characterization for trifluoromethanesulfonate (triflate) salts of the first definitive examples of cyclotriphosphinophosphonium and cyclodiphosphinophosphonium cations are described, representing new prototypical frameworks in the rational and systematic development of catena-phosphorus chemistry. Addition of methyl triflate (MeOTf) or triflic acid (HOTf) to cyclotetraphosphines (tBuP)4 (1a) or (CyP)4 (1b) gives [(tBuP)3PtBuMe][OTf] (2a[OTf]), [(CyP)3PCyMe][OTf] (2b[OTf]), [(tBuP)3PtBuH][OTf] (3a[OTf]), and [(CyP)3PCyH][OTf] (3b[OTf]), respectively. Cyclotriphosphine (tBuP)3 (4a) reacts with HOTF or Me2PCl/Me3SiOTf to give the ring expanded cations 3a[OTf] and [(tBuP)3PMe2][OTf] (5[OTf]), respectively, but reactions with MeOTf and HCl give cyclic diphosphinophosphonium cation [(tBuP)2PtBuMe][OTf] (6a[OTf]) and ring-opened triphosphine HtBuP-PtBu-PtBuCl (7), respectively. The analogous diphosphinophosphonium cation [(CyP)2PCyMe][OTf] (6b[OTf]) is formed along with 2b[OTf] in reactions of MeOTf with (CyP)3 (4b). Compounds 2a[OTf], 2b[OTf], 3a[OTf], 5[OTf], and 6a[OTf] have been crystallographically characterized. 1H NMR spectra of 2a[OTf], 2b[OTf], 5[OTf], and 6a[OTf] demonstrate that 3JPH coupling is only observed for methyl protons if they are in a cis orientation to the lone pairs on the adjacent phosphine sites.     

Substitution reactions of [Ru(dppe)(CO)(H(2)O)(3)][OTf](2)

The labile nature of the coordinated water ligands in the organometallic aqua complex [Ru(dppe)(CO)(H(2)O)(3)][OTf](2) (1) (dppe = Ph(2)PCH(2)CH(2)PPh(2); OTf = OSO(2)CF(3)) has been investigated through substitution reactions with a range of incoming ligands. Dissolution of 1 in acetonitrile or dimethyl sulfoxide results in the facile displacement of all three waters to give [Ru(dppe)(CO)(CH(3)CN)(3)][OTf](2) (2) and [Ru(dppe)(CO)(DMSO)(3)][OTf](2) (3), respectively. Similarly, 1 reacts with Me(3)CNC to afford [Ru(dppe)(CO)(CNCMe(3))(3)][OTf](2) (4). Addition of 1 equiv of 2,2'-bipyridyl (bpy) or 4,4'-dimethyl-2,2'-bipyridyl (Me(2)bpy) to acetone/water solutions of 1 initially yields [Ru(dppe)(CO)(H(2)O)(bpy)][OTf](2) (5a) and [Ru(dppe)(CO)(H(2)O)(Me(2)bpy)][OTf](2) (6a), in which the coordinated water lies trans to CO. Compounds 5a and 6a rapidly rearrange to isomeric species (5b, 6b) in which the ligated water is trans to dppe. Further reactivity has been demonstrated for 6b, which, upon dissolution in CDCl(3), loses water and coordinates a triflate anion to afford [Ru(dppe)(CO)(OTf)(Me(2)bpy)][OTf] (7). Reaction of 1 with CH(3)CH(2)CH(2)SH gives the dinuclear bridging thiolate complex [[(dppe)Ru(CO)](2)(mu-SCH(2)CH(2)CH(3))(3)][OTf] (8). The reaction of 1 with CO in acetone/water is slow and yields the cationic hydride complex [Ru(dppe)(CO)(3)H][OTf] (9) via a water gas shift reaction. Moreover, the same mechanism can also be used to account for the previously reported synthesis of 1 upon reaction of Ru(dppe)(CO)(2)(OTf)(2) with water (Organometallics 1999, 18, 4068).     

A hemilabile binucleating pincer ligand for self-assembly of coordination oligomers and polymers

The bis(PNP)-donor pincer ligand 1,4-C(6)H(4){N(CH(2)CH(2)PPh(2))(2)}(2), 1, contains weakly basic nitrogen donor atoms because the lone pairs of electrons are conjugated to the bridging phenylene group, and this feature is used in the synthesis of oligomers and polymers. The complexes [Pd(2)X(2)(mu-1)](OTf)(2), X=Cl, Br or OTf, contain the ligand 1 in bis(pincer) binding mode (mu-kappa(6)-P(4)N(2)), but [Pd(4)Cl(6)(mu(3-)1)(2)]Cl(2) contains the ligand in an unusual unsymmetrical mu(3)-kappa(5)-P(4)N binding mode. The bromide complex is suggested to exist as a polymer [{Pd(2)Br(4)(mu(4)-1)}(n)] with the ligands 1 in mu(4)-kappa(4)-P(4) binding mode. The methylplatinum(II) complexes [Pt(2)Me(4)(mu-1)] and [Pt(2)Me(2)(mu-1)](O(2)CCF(3))(2) contain the ligand in mu-kappa(4)-P(4) and mu-kappa(6)-P(4)N(2) bonding modes, while the silver(I) complex [Ag(2)(O(2)CCF(3))(2) (mu-1)] contains the ligand 1 in an intermediate bonding mode in which the nitrogen donors are very weakly coordinated. The complexes [Pd(2)(OTf)(2)(mu-1)](OTf)(2) and [Ag(2)(O(2)CCF(3))(2)(mu-1)] react with 4,4'-bipyridine to give polymers [Pd(2)(micro-bipy)(mu-1)](OTf)(4) and [Ag(2)(mu-bipy)(mu-1)](O(2)CCF(3))(2).     

Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands

Reaction of sodium hydrotris(methimazolyl)borate (NaTm(Me)) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm(Me))X] (X = Cl, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(Tm(Me))(2)](+) and [Co(2)(Tm(Me))(2)X](+) in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(Tm(Me))(2)](+) cation, which has been crystallographically characterized as the BF(4)(-), ClO(4)(-), Br(-), and I(-), salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm(Me))](+), resulted in ligand decomposition to yield [Co(mtH)(3)I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp(Me)) ligand, [Co(Cp(Me))(Tm(Me))]I was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) Tm(Me) complexes are consistently more difficult to reduce than their Tp and Cp congeners.