Preparation of five- and six-coordinate aryl(hydrido) iridium(III) complexes from benzene and functionalized arenes by C-H activation

The reaction of the in situ generated cyclooctene iridium(I) derivative trans-[IrCl(C8H14)(PiPr3)2] with benzene at 80 degrees C gave a mixture of the five-coordinate dihydrido and hydrido(phenyl) iridium(III) complexes [IrH2(Cl)(PiPr3)2] 2 and [IrH(C6H5)(Cl)(PiPr3)2] 3 in the ratio of about 1 : 2. The chloro- and fluoro-substituted arenes C6H5X (X = Cl, F), C6H4F2 and C6H4F(CH3) reacted also by C-H activation to afford the corresponding aryl(hydrido) iridium(III) derivatives [IrH(C6H4X)(Cl)(PiPr3)2] 7, 8, [IrH(C6H3F2)(Cl)(PiPr3)2] 9-11 and [IrH[C6H3F(CH3)](Cl)(PiPr3)2] 12, 13, respectively. The formation of isomeric mixtures had been detected by 1H, 13C, 19F and 31P NMR spectroscopy. Treatment of 3 and 7-13 with CO gave the octahedral carbonyl iridium(III) complexes [IrH(C6H3XX')(Cl)(CO)(PiPr3)2] 5, 14-20 without the elimination of the arene. The reactions of trans-[IrCl(C8H14)(PiPr3)2] with aryl ketones C6H5C(O)R (R = Me, Ph), aryl ketoximes C6H5C(NOH)R (R = Me, Ph) and benzaloxime C6H5C(NOH)H resulted in the formation of six-coordinate aryl(hydrido) iridium(III) compounds 21-25 with the aryl ligand coordinated in a bidentate kappa2-C,O or kappa2-C,N fashion. With C6H5C(O)NH2 as the substrate, the two isomers [IrH[kappa2-N,O-NHC(O)C6H5](Cl)(PiPr3)2] 26 and [IrH[kappa2-C,O-C6H4C(O)NH2](Cl)(PiPr3)2] 27 were prepared stepwise. Treatment of trans-[IrCl(C8H14)(PiPr3)2] with benzoic acid gave the benzoato(hydrido) complex [IrH[kappa2-O,O-O2CC6H5](Cl)(PiPr3)2] 29 which did not rearrange to the kappa2-C,O isomer.     

Molecular dynamics of haloalkane corral formation and surface halogenation at Si(111)-7 x 7

Long-chain organic molecules, 1-halododecane, RX (X = Cl,Br), adsorbed on Si(111)-7 x 7 were shown to form stable dimeric corrals; type I around corner holes and type II around corner adatoms S. Dobrin et al. [Surf. Sci. Lett. 600, L43 (2006)]. Here we examine the molecular dynamics of corral formation, in which mobile physisorbed adsorbates spontaneously convert to immobile. At high coverage the mechanism gives evidence of involving collisions between mobile vertical monomers, giving types I and II immobile horizontal dimers, vD +vD -->h2 (I, II). At low coverage mobile vertical monomers collide with immobile horizontal ones to form largely type-II corrals, vD + h-->h2 (II). Thermal reaction of corrals with X = Br brominates the surface by two distinct molecular pathways, thought to have more general applicability: "daughter-mediated" reaction of vertical v(A) with a low activation energy (here Ea approximately 5 kcal mol(-1)) and "parent-mediated" reaction of horizontal h or h2 with high activation energy (here Ea = 29 kcal mol(-1)).     

Influence of ligand polarizability on the reversible binding of O2 by trans-[Rh(X)(XNC)(PPh3)2] (X = Cl, Br, SC6F5, C2Ph; XNC = xylyl isocyanide). Structures and a kinetic study

The complexes trans-[Rh(X)(XNC)(PPh 3) 2] (X = Cl, 1; Br, 2; SC 6F 5, 3; C 2Ph, 4; XNC = xylyl isocyanide) combine reversibly with molecular oxygen to give [Rh(X)(O 2)(XNC)(PPh 3) 2] of which [Rh(SC 6F 5)(O 2)(XNC)(PPh 3) 2] ( 7) and [Rh(C 2Ph)(O 2)(XNC)(PPh 3) 2] ( 8) are sufficiently stable to be isolated in crystalline form. Complexes 2, 3, 4, and 7 have been structurally characterized. Kinetic data for the dissociation of O 2 from the dioxygen adducts of 1- 4 were obtained using (31)P NMR to monitor changes in the concentration of [Rh(X)(O 2)(XNC)(PPh 3) 2] (X = Cl, Br, SC 6F 5, C 2Ph) resulting from the bubbling of argon through the respective warmed solutions (solvent chlorobenzene). From data recorded at temperatures in the range 30-70 degrees C, activation parameters were obtained as follows: Delta H (++) (kJ mol (-1)): 31.7 +/- 1.6 (X = Cl), 52.1 +/- 4.3 (X = Br), 66.0 +/- 5.8 (X = SC 6F 5), 101.3 +/- 1.8 (X = C 2Ph); Delta S (++) (J K (-1) mol (-1)): -170.3 +/- 5.0 (X = Cl), -120 +/- 13.6 (X = Br), -89 +/- 18.2 (X = SC 6F 5), -6.4 +/- 5.4 (X = C 2Ph). The values of Delta H (++) and Delta S (++) are closely correlated (R (2) = 0.9997), consistent with a common dissociation pathway along which the rate-determining step occurs at a different position for each X. Relative magnitudes of Delta H (++) are interpreted in terms of differing polarizabilities of ligands X.     

Synthesis of carbaalane halogen derivatives

The carbaalane halogen derivatives [(AlX)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (X = F (9), Cl (7), Br (10), I (11)) were prepared in toluene from [(AlH)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (6) and BF(3).OEt(2), BX(3) (X = Br, I), Me(3)SnF, and Me(3)SiX (X = Cl, Br, I), respectively. A partially halogenated product [(AlH)(2)(AlX)(4)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (12) (X = Cl (approximately 40%), Br (approximately 60%)) was obtained from 5 and impure BBr(3). [(AlH)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (5) was converted to [(AlX)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (X = F (13), Cl (14), Br (15), I (16)) using BF(3).OEt(2) and Me(3)SiX (X = Cl, Br, I), respectively. The X-ray single-crystal structures of 11.C(6)H(6), 12.3C(7)H(8), 13.6C(7)H(8), and 15.4C(7)H(8) were determined. Compounds 7 and 9-11 are soluble in benzene/toluene and could be well characterized by NMR spectroscopy and MS (EI) spectrometry. The results demonstrate the facile substitution of the hydridic hydrogen atoms in 5 and 6 by the halides with different reagents.     

Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium

Reaction of the proligand Ph2PN(SiMe3)2 (L1) with WCl6 gives the oligomeric phosphazene complex [WCl4(NPPh2)]n, 1 and subsequent reaction with PMe2Ph or NBu4Cl gives [WCl4(NPPh2)(PMe2Ph)] (2) or [WCl5(NPPh2)][NBu4] (3), respectively. DF calculations on [WCl5(NPPh2)][NBu4] show a W=N double bond (1.756 A) and a P-N bond distance of 1.701 A, which combined with the geometry about the P atom suggests, there is no P-N multiple bonding. Reaction of L1 with [ReOX3(PPh3)2] in MeCN (X = Cl or Br) gives [ReX2(NC(CH3)P(O)Ph2)(MeCN)(PPh3)](X = Cl, 4, X = Br, 5) which contains the new phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6 degrees, when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2(L2H) reacts with [(C5H5)TiCl3] to give [(C5H5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen atoms. Reaction of the proligands Ph2PNHNR2[R2 = Me2 (L2H), -(CH2CH2)2NCH3 (L3H), (CH2CH2)2CH2 (L4H)] with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave [RuCl2(eta6-p-MeC6H4iPr)L] {L = L2H (7), L3H (8), L4H (9)}. The X-ray crystal structures of 7-9 confirmed that the phosphinohydrazine ligand is neutral and bound via the phosphorus only. Reaction of complexes 7-9 with AgBF4 resulted in chloride ion abstraction and the formation of the cationic species [RuCl(6-p-MeC6H4iPr)(L)]+ BF4- {(L = L2H (10), L3H (11), L4H (12)}. Finally, reaction of complex 6 with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave the binuclear species [(eta6-p-MeC6H4iPr)Cl2Ru(mu2,eta3-Ph2PNNMe2)TiCl2(C5H5)], 13.     

Triangular,ferromagnetically-coupled CuII 3-pyrazolato complexes as possible models of particulate methane monooxygenase (pMMO)

Magnetic susceptibility and EPR studies show that trinuclear Cu(II)-pyrazolato complexes with a Cu(3)(mu3-X)2 core (X = Cl, Br) are ferromagnetically coupled: J(Cu-Cu) = +28.6 cm(-1) (X = Cl), +3.1 cm(-1) (X = Br). The orderly transition from an antiferromagnetic to a ferromagnetic exchange among the Cu centers of Cu(3)(mu3-X) complexes, X = O, OH, Cl, Br, follows the change of the Cu-X-Cu angle from 120 degrees to approximately 80 degrees. The crystal structures of [Bu4N]2"[Cu3(mu3-Br)2(mu-pz*)3Br3] (pz* = pz (1a) or 4-O2N-pz (1b), pz = pyrazolato anion, C(3)H(3)N(2)(1-)) are presented.     

Symmetric and asymmetric dinuclear manganese(IV) complexes possessing a [MnIV2(mu-O)2(muO2CMe)]3+ core and terminal Cl- ligands

The synthesis of new dinuclear manganese(IV) complexes possessing the [Mn(IV)(2)(mu-O)(2)(mu-O(2)CMe)](3+) core and containing halide ions as terminal ligands is reported. [Mn(2)O(2)(O(2)CMe)Cl(2)(bpy)(2)](2)[MnCl(4)] (1; bpy = 2,2'-bipyridine) was prepared by sequential addition of [MnCl(3)(bpy)(H(2)O)] and (NBzEt(3))(2)[MnCl(4)] to a CH(2)Cl(2) solution of [Mn(3)O(4)(O(2)CMe)(4)(bpy)(2)]. The complex [Mn(IV)(2)O(2)(O(2)CMe)Cl(bpy)(2)(H(2)O)](NO(3))(2) (2) was obtained from a water/acetic acid solution of MnCl(2).4H(2)O, bpy, and (NH(4))(2)[Ce(NO(3))(6)], whereas the [Mn(IV)(2)O(2)(O(2)CR)X(bpy)(2)(H(2)O)](ClO(4))(2) [X = Cl(-) and R = Me (3), Et (5), or C(2)H(4)Cl (6); and X = F(-), R = Me (4)] were prepared by a slightly modified procedure that includes the addition of HClO(4). For the preparation of 4, MnF(2) was employed instead of MnCl(2).4H(2)O. [Mn(2)O(2)(O(2)CMe)Cl(2)(bpy)(2)](2)[MnCl(4)].2CH(2)Cl(2) (1.2CH(2)Cl(2)) crystallizes in the monoclinic space group C2/c with a = 21.756(2) A, b = 12.0587(7) A, c = 26.192(2) A, alpha = 90 degrees, beta = 111.443(2) degrees, gamma = 90 degrees, V = 6395.8(6) A(3), and Z = 4. [Mn(2)O(2)(O(2)CMe)Cl(H(2)O)(bpy)(2)](NO(3))(2).H(2)O (2.H(2)O) crystallizes in the triclinic space group Ponemacr; with a = 11.907(2) A, b = 12.376(2) A, c = 10.986(2) A, alpha = 108.24(1) degrees, beta = 105.85(2) degrees, gamma = 106.57(1) degrees, V = 1351.98(2) A(3), and Z = 2. [Mn(2)O(2)(O(2)CMe)Cl(H(2)O)(bpy)(2)](ClO(4))(2).MeCN (3.MeCN) crystallizes in the triclinic space group Ponemacr; with a = 11.7817(7) A, b = 12.2400(7) A, c = 13.1672(7) A, alpha = 65.537(2) degrees, beta = 67.407(2) degrees, gamma = 88.638(2) degrees, V = 1574.9(2) A(3), and Z = 2. The cyclic voltammogram (CV) of 1 exhibits two processes, an irreversible oxidation of the [MnCl(4)](2)(-) at E(1/2) approximately 0.69 V vs ferrocene and a reversible reduction at E(1/2) = 0.30 V assigned to the [Mn(2)O(2)(O(2)CMe)Cl(2)(bpy)(2)](+/0) couple (2Mn(IV) to Mn(IV)Mn(III)). In contrast, the CVs of 2 and 3 show only irreversible reduction features. Solid-state magnetic susceptibility (chi(M)) data were collected for complexes 1.1.5H(2)O, 2.H(2)O, and 3.H(2)O in the temperature range 2.00-300 K. The resulting data were fit to the theoretical chi(M)T vs T expression for a Mn(IV)(2) complex derived by use of the isotropic Heisenberg spin Hamiltonian (H = -2JS(1)S(2)) and the Van Vleck equation. The obtained fit parameters were (in the format J/g) -45.0(4) cm(-)(1)/2.00(2), -36.6(4) cm(-)(1)/1.97(1), and -39.3(4) cm(-)(1)/1.92(1), respectively, where J is the exchange interaction parameter between the two Mn(IV) ions. Thus, all three complexes are antiferromagnetically coupled.     

Syntheses and reactions of hexavalent organotellurium compounds bearing five or six tellurium-carbon bonds

A variety of hexaorganotellurium compounds, Ar(6-n)(CH3)nTe [Ar=4-CF3C6H4, n=0 (1a), n=1 (3a), n=2 (trans-4a and cis-4a), n=3 (mer-5a), n=4 (trans-6a); Ph, n=0 (1b), n=1 (3b), n=2 (trans-4b); 4-CH3C6H4, n=0 (1c), n=1 (3c), n=2 (trans-4c), n=4 (trans-6c); 4-BrC6H4, n=0 (1d)] and Ar5(R)Te [Ar=4-CF3C6H4, R=4-CH3OC6H4 (8); Ar=4-CF3C6H4, R=vinyl (9), Ar=Ph, R=vinyl (10), Ar=4-CF3C6H4, R=PhSCH2 (11), Ar=Ph, R=PhSCH2 (12), Ar=4-CF3C6H4, R=nBu (13)] and pentaorganotellurium halides, Ar5TeX [Ar=4-CF3C6H4, X=Cl (2a-Cl), X=Br (2a-Br); Ar=Ph, X=Cl (2b-Cl), X=Br (2b-Br); Ar=4-CH3C6H4, X=Cl (2c-Cl), X=Br (2c-Br); Ar=4-BrC6H4, X=Br (2d-Br)] and (4-CF3C6H4)4(CH3)TeX [X=Cl (trans-7a-Cl) and X=Br (trans-7a-Br)] were synthesized by the following methods: 1) one-pot synthesis of 1 a, 2) the reaction of SO2Cl2 or Br2 with Ar5Te(-)Li+ generated from TeCl4 or TeBr4 with five equivalents of ArLi, 3) reductive cleavage of Ar(6-m)(CH3)(m)Te (m=0 or 2) with KC8 followed by treatment with CH3I, 4) valence expansion reaction from low-valent tellurium compounds by treatment with KC8 followed by reaction with CH3I, 5) nucleophilic substitution of Ar(6-y-z)(CH3)zTeX(y-z) (X=Cl, Br, OTf; z=0, 1; y=1, 2) with organolithium reagents. The scope and limitations and some details for each method are discussed and electrophilic halogenation of the hexaorganotellurium compounds is also described.     

On the reactivity toward ketones of new methyl amino complexes of Rh(III) and Ag(I). Synthesis of ortho-rhodiated acetophenone methyl imine complexes

MeNH(2) reacts with silver salts AgX (2:1) to give [Ag(NH(2)Me)(2)]X [X = TfO = CF(3)SO(3) (1.TfO) and ClO(4) (1.ClO(4))]. Neutral mono(amino) Rh(III) complexes [Rh(Cp*)Cl(2)(NH(2)R)] [R = Me (2a), To = C(6)H(4)Me-4 (2b)] have been prepared by reacting [Rh(Cp*)Cl(mu-Cl)](2) with RNH(2) (1:2). The following cationic methyl amino complexes have also been prepared: [Rh(Cp*)Cl(NH(2)Me)(PPh(3))]TfO (3.TfO), from [Rh(Cp*)Cl(2)(PPh(3))] and 1.TfO (1:1); [Rh(Cp*)Cl(NH(2)R)2]X, where R = Me, X = Cl, (4a.Cl), from [Rh(Cp*)Cl(mu-Cl)]2 and MeNH2 (1:4), or R = Me, X = ClO4 (4a.ClO4), from 4a.Cl and NaClO4 (1:4.8), or R = To, X = TfO (4b.TfO), from [Rh(Cp*)Cl(mu-Cl)](2), ToNH(2) and TlTfO (1:4:2); [Rh(Cp*)(NH(2)Me)(tBubpy)](TfO)(2) (tBubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, 5.TfO), from 2a, TlTfO and tBubpy (1:2:1); [Rh(Cp*)(NH(2)Me)(3)](TfO)2 (6.TfO) from [Rh(Cp*)Cl(mu-Cl)](2) and 1.TfO (1:4). 2-6 constitute the first family of methyl amino complexes of rhodium. 1 and 4a.ClO(4) react with acetone to give, respectively, the methyl imino complexes [Ag{N(Me)=CMe(2)}()]X [X = TfO (7.TfO), ClO(4) (7.ClO(4))], and [Rh(Cp*)Cl(Me-imam)]ClO(4) [8.ClO(4), Me-imam = N,N'-N(Me)=C(Me)CH(2)C(Me)(2)NHMe]. 7.X (X = TfO, ClO(4)) are new members of the small family of methyl acetimino complexes of any metal whereas 8.ClO4 results after a double acetone condensation to give the corresponding bis(methyl acetimino) complex and an aldol-like condensation of the two imino ligands. The acetimino complex [Ag(NH=CMe(2))(2)]ClO(4) reacts with [Rh(Cp*)Cl(imam)]ClO(4) [1:1, imam = N,N'-NH=C(Me)CH(2)C(Me)(2)NH(2)] to give [Rh(Cp*)(imam)(NH=CMe(2))](ClO(4))(2) (9a.ClO(4)). 8.ClO(4) reacts with AgClO(4) (1:1) in MeCN to give [Rh(Cp*)(Me-imam)(NCMe)](ClO(4))2 (9b.ClO(4)), which in turn reacts with XyNC (Xy = C(6)H(3)Me(2)-2,6) or with MeNH(2) (1:1) to give [Rh(Cp*)(Me-imam)L](ClO(4))(2) [L = XyNC (9c.ClO(4)), MeNH(2) (9d.ClO(4))]. 6.TfO reacts with acetophenone to give [Rh(Cp*){C,N-C(6)H(4)C(Me)=N(Me)-2}(NH(2)Me)]TfO (10a.TfO), the first complex resulting from such a condensation and cyclometalation reaction. In turn, 10a.TfO reacts with isocyanides RNC (1:1) at room temperature to give [Rh(Cp*){C,N-C(6)H(4)C(Me)=NMe-2}(CNR)]TfO [R = tBu (10b.TfO), Xy (10c.TfO)], or 1:12 at 60 degrees C to give [Rh(Cp*){C,N-C(=NXy)C(6)H(4)C(Me)=N(Me)-2}(CNXy)]TfO (11.TfO). The crystal structures of 9a.ClO(4).acetone-d6, 9c.ClO(4), and 10a.TfO have been determined.     

Rhenium(I) carbonyl complexes of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPT). Rhenium(I)-promoted methoxylation of the triazine ring carbon atom in dinuclear rhenium complexes

2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPT) bridged dinuclear rhenium(I) tricarbonyl halide complexes with the composition (mu-TPT)[ReX(CO)(3)](2) (3, X = Cl; 4, X = Br) can be made either by one-pot reaction of TPT with 2 equiv of [ReX(CO)(5)] (X = Cl and Br) in chloroform or by reacting mononuclear [ReX(CO)(3)(TPT)] (2) (1, X = Cl; 2, X = Br) with an excess amount of [ReX(CO)(5)]. Crystal data are as follows. 1: monoclinic, P2(1)/c, a = 11.751(1) A, b = 11.376(1) A, c = 15.562(2) A, beta = 103.584(2) degrees, V = 2022.0(4) A(3), Z = 4. 2: monoclinic, P2(1)/c, a = 11.896(1) A, b = 11.396(1) A, c = 15.655(1) A, beta = 104.474(2) degrees, V = 2054.9(3) A(3), Z = 4. 3: triclinic, P1, a = 11.541(2) A, b = 12.119(2) A, c = 13.199(2) A, alpha = 80.377(2) degrees, beta = 76.204(3) degrees, gamma = 66.826(2) degrees, V = 1642.5(4) A(3), Z = 2. Crystals of 4 crystallized from acetone: triclinic, P1, a = 11.586(5) A, b = 12.144(5) A, c = 13.364(6) A, alpha = 80.599(7) degrees, beta = 76.271(8) degrees, gamma = 67.158(8) degrees, V = 1678.0(12) A(3), Z = 2. Crystals of 4' are obtained from CH(2)Cl(2)-pentane solution: monoclinic, C2/c, a = 17.555(4) A, b = 15.277(3) A, c = 13.093(3) A, beta = 111.179(3) degrees, V = 3274.0(12) A(3), Z = 4. By contrast, similar reactions in the presence of methanol yielded complexes with the composition [mu-C(3)N(3)(OMe)(py)(2)(pyH)][ReX(CO)(3)](2) (5, X = Cl; 6, X = Br). Crystal data for 5: monoclinic, C2/c, a = 26.952(2) A, b = 16.602(1) A, c = 14.641(1) A, beta = 116.147(1) degrees, V = 5880.5(8) A(3), Z = 8. 6: monoclinic, C2/c, a = 27.513(3) A, b = 16.740(2) A, c = 14.837(2) A, beta = 116.925(2) degrees, V = 6092.8(10) A(3), Z = 8. An unusual metal-induced methoxylation at the carbon atom of the triazine ring of the bridging TPT ligand was observed. The nucleophilic attack of MeO(-) on C(3) results in a tetrahedral geometry around the carbon atom. Concomitantly, the uncoordinated pyridyl ring is protonated and rotated into a perpendicular orientation relative to the central C(3)N(3) ring. Reaction of TPT with [NEt(4)](2)[ReBr(3)(CO)(3)] in benzene-methanol resulted in an unexpected dinuclear complex 7, with formulation [mu-C(3)N(3)(OMe)(py)(3)][Re(CO)(3)][ReBr(CO)(3)]. The methoxylated TPT ligand functions simultaneously as a tridentate and bidentate ligand with two fac-Re(CO)(3)(+) cores. Crystal data for 7: monoclinic, P2(1)/n, a = 12.114(1) A, b = 14.878(1) A, c = 15.807(1) A, beta = 104.601(1) degrees, V = 2756.9(3) A(3), Z = 4.     

Synthesis, Structure, and Reactivity of [Zr(6)Cl(18)H(5)](2)(-), the First Paramagnetic Species of Its Class

Reaction of [Zr(6)Cl(18)H(5)](3)(-) (1) with 1 equiv of TiCl(4) yields a new cluster anion, [Zr(6)Cl(18)H(5)](2)(-) (2), which can be converted back into [Zr(6)Cl(18)H(5)](3)(-) (1) upon addition of 1 equiv of Na/Hg. Cluster 2 is paramagnetic and unstable in the presence of donor molecules. It undergoes a disproportionation reaction to form 1, some Zr(IV) compounds, and H(2). It also reacts with TiCl(4) to form [Zr(2)Cl(9)](-) (4) and a tetranuclear mixed-metal species, [Zr(2)Ti(2)Cl(16)](2)(-) (3). The oxidation reaction of 1 with TiCl(4) is unique. Oxidation of 1 with H(+) in CH(2)Cl(2) solution results in the formation of [ZrCl(6)](2)(-) (5) and H(2), while in py solution the oxidation product is [ZrCl(5)(py)](-) (6). There is no reaction between 1 and TiI(4), ZrCl(4), [TiCl(6)](2)(-), [ZrCl(6)](2)(-), or CrCl(3). Compounds [Ph(4)P](2)[Zr(6)Cl(18)H(5)] (2a), [Ph(4)P](2)[Zr(2)Ti(2)Cl(16)] (3a), [Ph(4)P](2)[Zr(2)Cl(9)] (4a), [Ph(4)P](2)[ZrCl(6)].4MeCN (5a.4MeCN), and [Ph(4)P][ZrCl(5)(py)] (6a) were characterized by X-ray crystallography. Compound 2a crystallized in the trigonal space group R&thremacr; with cell dimensions (20 degrees C) of a = 28.546(3) ?, b = 28.546(3) ?, c = 27.679(2) ?, V = 19533(3) ?(3), and Z = 12. Compound 3a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 11.375(3) ?, b = 13.357(3) ?, c = 11.336(3) ?, alpha = 106.07(1) degrees, beta = 114.77(1) degrees, gamma = 88.50(1) degrees, V = 1494.8(7) ?(3), and Z = 1. Compound 4a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 12.380(5) ?, b = 12.883(5) ?, c = 11.000(4) ?, alpha = 110.39(7) degrees, beta = 98.29(7) degrees, gamma = 73.12(4) degrees, V = 1572(1) ?(3), and Z = 2. Compound 5a.4MeCN crystallized in the monoclinic space group P2(1)/c with cell dimensions (-60 degrees C) of a = 9.595(1) ?, b = 19.566(3) ?, c = 15.049(1) ?, beta = 98.50(1) degrees, V = 2794.2(6) ?(3), and Z = 2. Compound 6a crystallized in the monoclinic space group P2(1)/c with cell dimensions (20 degrees C) of a = 10.3390(7) ?, b = 16.491(2) ?, c = 17.654(2) ?, beta = 91.542(6) degrees, V = 3026.4(5) ?(3), and Z = 4.     

Organometallic uranium(V)-imido halide complexes: from synthesis to electronic structure and bonding

Reaction of (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2) or (C5Me5)2U(=N-2,6-(i)Pr2-C6H3)(THF) with 5 equiv of CuX(n) (n = 1, X = Cl, Br, I; n = 2, X = F) affords the corresponding uranium(V)-imido halide complexes, (C5Me5)2U(=N-Ar)(X) (where Ar = 2,4,6-(t)Bu3-C6H2 and X = F (3), Cl (4), Br (5), I (6); Ar = 2,6-(i)Pr2-C6H3 and X = F (7), Cl (8), Br (9), I (10)), in good isolated yields of 75-89%. These compounds have been characterized by a combination of single-crystal X-ray diffraction, (1)H NMR spectroscopy, elemental analysis, mass spectrometry, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. The uranium L(III)-edge X-ray absorption spectrum of (C5Me5)2U(=N-2,4,6-(t)Bu3-C6H2)(Cl) (4) was analyzed to obtain structural information, and the U=N imido (1.97(1) A), U-Cl (2.60(2) A), and U-C5Me5 (2.84(1) A) distances were consistent with those observed for compounds 3, 5, 6, 8-10, which were all characterized by single-crystal X-ray diffraction studies. All (C5Me5)2U(=N-Ar)(X) complexes exhibit U(V)/U(IV) and U(VI)/U(V) redox couples by voltammetry, with the potential separation between these metal-based couples remaining essentially constant at approximately 1.50 V. The electronic spectra are comprised of pi-->pi* and pi-->nb(5f) transitions involving electrons in the metal-imido bond, and metal-centered f-f bands illustrative of spin-orbit and crystal-field influences on the 5f(1) valence electron configuration. Two distinct sets of bands are attributed to transitions derived from this 5f(1) configuration, and the intensities in these bands increase dramatically over those found in spectra of classical 5f(1) actinide coordination complexes. Temperature-dependent magnetic susceptibilities are reported for all complexes with mu(eff) values ranging from 2.22 to 2.53 mu(B). The onset of quenching of orbital angular momentum by ligand fields is observed to occur at approximately 40 K in all cases. Density functional theory results for the model complexes (C5Me5)2U(=N-C6H5)(F) (11) and (C5Me5)2U(=N-C6H5)(I) (12) show good agreement with experimental structural and electrochemical data and provide a basis for assignment of spectroscopic bands. The bonding analysis describes multiple bonding between the uranium metal center and imido nitrogen which is comprised of one sigma and two pi interactions with variable participation of 5f and 6d orbitals from the uranium center.     

Diverse solid-state and solution structures within a series of hexaamine dicopper(II) complexes

Mono- and dicopper(II) complexes of a series of potentially bridging hexaamine ligands have been prepared and characterized in the solid state by X-ray crystallography. The crystal structures of the following Cu(II) complexes are reported: [Cu(HL3)](ClO4)(3), C11H31Cl3CuN6O12, monoclinic, P2(1)/n, a = 8.294(2) A, b = 18.364(3) A, c = 15.674(3) A, beta = 94.73(2) degrees, Z = 4; ([Cu2(L4)(CO3)](2))(ClO4)(4).4H2O, C40H100Cl4Cu4N12O26, triclinic, P1, a = 9.4888(8) A, b = 13.353(1) A, c = 15.329(1) A, alpha = 111.250(7) degrees, beta = 90.068(8) degrees, gamma = 105.081(8) degrees, Z = 1; [Cu2(L5)(OH2)(2)](ClO4)(4), C13H36Cl4Cu2N6O18, monoclinic, P2(1)/c, a = 7.225(2) A, b = 8.5555(5) A, c = 23.134(8) A, beta = 92.37(1) degrees, Z = 2; [Cu2(L6)(OH2)(2)](ClO4)(4).3H2O, C14H44Cl4Cu2N6O21, monoclinic, P2(1)/a, a = 15.204(5) A, b = 7.6810(7) A, c = 29.370(1) A, beta = 100.42(2) degrees, Z = 4. Solution spectroscopic properties of the bimetallic complexes indicate that significant conformational changes occur upon dissolution, and this has been probed with EPR spectroscopy and molecular mechanics calculations.     

Bridging nitrate groups in [Mn(4)O(3)(NO(3))(O(2)CMe)(3)(R(2)dbm)(3)] (R = H, Et) and [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)): acidolysis routes to tetranuclear manganese carboxylate complexes

New synthesis procedures are described to tetranuclear manganese carboxylate complexes containing the [Mn(4)O(2)](8+) or [Mn(4)O(3)X](6+) (X(-) = MeCO(2)(-), F(-), Cl(-), Br(-), NO(3)(-)) core. These involve acidolysis reactions of [Mn(4)O(3)(O(2)CMe)(4)(dbm)(3)] (1; dbm is the anion of dibenzoylmethane) or [Mn(4)O(2)(O(2)CEt)(6)(dbm)(2)] (8) with HX (X(-) = F(-), Cl(-), Br(-), NO(3)(-)); high-yield routes to 1 and 8 are also described. The X(-) = NO(3)(-) complexes [Mn(4)O(3)(NO(3))(O(2)CR)(3)(R'(2)dbm)(3)] (R = Me, R' = H (6); R = Me, R' = Et (7); R = Et, R' = H (12)) represent the first synthesis of the [Mn(4)O(3)(NO(3))](6+) core, which contains an unusual eta(1):mu(3)-NO(3)(-) group. Treatment of known [Mn(4)O(2)(O(2)CEt)(7)(bpy)(2)](ClO(4)) with HNO(3) gives [Mn(4)O(2)(NO(3))(O(2)CEt)(6)(bpy)(2)](ClO(4)) (15) containing a eta(1):eta(1):mu-NO(3)(-) group bridging the two body Mn(III) ions of the [Mn(4)O(2)](8+) butterfly core. Complex 7 x 4CH(2)Cl(2) crystallizes in space group P2(1)2(1)2(1) with (at -168 degrees C) a = 21.110(3) A, b = 22.183(3) A, c = 15.958(2) A, Z = 4, and V = 7472.4(3) A(3). Complex 15 x (3)/(2)CH(2)Cl(2) crystallizes in space group P2(1)/c with (at -165 degrees C) a = 26.025(4) A, b = 13.488(2) A, c = 32.102(6) A, beta = 97.27(1) degrees, Z = 8, and V = 11178(5) A(3). Complex 7 contains a [Mn(4)(mu(3)-O)(3)(mu(3)-NO(3))](6+) core (3Mn(III), Mn(IV)) as seen for previous [Mn(4)O(3)X](6+) complexes. Complex 15 contains a butterfly [Mn(4)(mu(3)-O)(2)](8+) core. (1)H NMR spectra have been recorded for all complexes reported in this work and the various resonances assigned. All complexes retain their structural integrity on dissolution in chloroform and dichloromethane. Magnetic susceptibility (chi(M)) data were collected on 12 in the 5-300 K range in a 10.0 kG (1 T) field. Fitting of the data to the theoretical chi(M) vs T expression appropriate for a [Mn(4)O(3)X](6+) complex of C(3)(v)() symmetry gave J(34) = -23.9 cm(-)(1), J(33) = 4.9 cm(-)(1), and g = 1.98, where J(34) and J(33) refer to the Mn(III)Mn(IV) and Mn(III)Mn(III) pairwise exchange interactions, respectively. The ground state of the molecule is S = 9/2, as found previously for other [Mn(4)O(3)X](6+) complexes. This was confirmed by magnetization data collected at various fields and temperatures. Fitting of the data gave S = 9/2, D = -0.45 cm(-1), and g = 1.96, where D is the axial zero-field splitting parameter.     

Synthesis and reactivity of Ir(I) and Ir(III) complexes with MeNH2, Me2C=NR (R = H, Me), C,N-C6H4{C(Me)=N(Me)}-2, and N,N'-RN=C(Me)CH2C(Me2)NHR (R = H, Me) ligands

Complexes [Ir(Cp*)Cl(n)(NH2Me)(3-n)]X(m) (n = 2, m = 0 (1), n = 1, m = 1, X = Cl (2a), n = 0, m = 2, X = OTf (3)) are obtained by reacting [Ir(Cp*)Cl(mu-Cl)]2 with MeNH2 (1:2 or 1:8) or with [Ag(NH2Me)2]OTf (1:4), respectively. Complex 2b (n = 1, m = 1, X = ClO 4) is obtained from 2a and NaClO4 x H2O. The reaction of 3 with MeC(O)Ph at 80 degrees C gives [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(NH2Me)]OTf (4), which in turn reacts with RNC to give [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(CNR)]OTf (R = (t)Bu (5), Xy (6)). [Ir(mu-Cl)(COD)]2 reacts with [Ag{N(R)=CMe2}2]X (1:2) to give [Ir{N(R)=CMe2}2(COD)]X (R = H, X = ClO4 (7); R = Me, X = OTf (8)). Complexes [Ir(CO)2(NH=CMe2)2]ClO4 (9) and [IrCl{N(R)=CMe2}(COD)] (R = H (10), Me (11)) are obtained from the appropriate [Ir{N(R)=CMe2}2(COD)]X and CO or Me4NCl, respectively. [Ir(Cp*)Cl(mu-Cl)]2 reacts with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give [Ir(Cp*)(mu-Cl)(NH=CMe2)]2(ClO4)2 (12) which in turn reacts with PPh 3 or Me4NCl (1:2) to give [Ir(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (13) or [Ir(Cp*)Cl2(NH=CMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give [Ir(Cp*)Cl2(NH3)] (15). The reaction of [Ir(Cp*)Cl(mu-Cl)]2 with [Ag(NH=CMe2)2]ClO4 (1:4) gives [Ir(Cp*)(NH=CMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3=P=N=PPh3) under different reaction conditions to give [Ir(Cp*)(NH=CMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give [Ir(Cp*)Cl(NH=CMe2)2]ClO4 (17), which in turn reacts with PPNCl to give [Ir(Cp*)Cl(H-imam)]Cl (R-imam = N,N'-N(R)=C(Me)CH2C(Me)2NHR (18a)]. Complexes [Ir(Cp*)Cl(R-imam)]ClO4 (R = H (18b), Me (19)) are obtained from 18a and AgClO4 or by refluxing 2b in acetone for 7 h, respectively. They react with AgClO4 and the appropriate neutral ligand or with [Ag(NH=CMe2)2]ClO4 to give [Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = (t)BuNC (20), XyNC (21); R = Me, L = MeCN (22)) or [Ir(Cp*)(H-imam)(NH=CMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give [Ir(Cp*)(H-imam)(NH=CMe2)]Cl(ClO4) (23b). The reaction of 22 with XyNC gives [Ir(Cp*)(Me-imam)(CNXy)](ClO4)2 (24). The structures of complexes 15, 16c and 18b have been solved by X-ray diffraction methods.     

Synthesis and structural studies of germyl and germyl/stannyl substituted tungstenocenes

One-pot reactions of [WCp2(H)2] and [WCp2(H)(SnMe3)] with "BuLi followed by an equivalent of GeMe2Cl2 afford mono(germyl) substituted tungstenocenes [WCp2(H)(GeMe2Cl)] (1) and [WCp2(SnMe3)(GeMe2Cl)] (7). Reactions of the products with tin halides in the presence NEt3 afford the mixed complexes [WCp2(SnR2X)(GeMe2Y)] (X, Y = Cl, Br, R = Me, Et), which were further converted to moderately stable compounds [WCp2(SnR2H)(GeMe2H)] (R = Me (10), Et (11)). A number of asymmetric mono(halo)-substituted germyl/stannyl tungstenocenes [WCp2(SnMe2X)(GeMe2H)] (X = Cl (12), Br (13)) and [WCp2(SnEt2Y)(GeMe2H)] (Y = Br (14), I (15)) were prepared by selective halogenation of the Sn-H bond in 10 and 11. X-Ray studies of [WCp2(H)(GeMe2Cl)] (1), [WCp2(SnEt2Br)(GeMe2Cl)] (4), and [WCp2(SnEt2Br)(GeMe2H)] (14) established classical structures of these compounds. X-Ray study of complex [WCp2(SnMeCl)(GeMe2Cl)] (3) revealed the presence of interligand Ge-Cl...Sn-Cl interactions in a highly Ge/Sn disordered structure. Analyses of molecular parameters of 1, 4, and 14 suggest the presence of a negative hyperconjugation between metal lone pairs and the sigma*-orbital of the E-X bond, which is stronger in bromo substituted complexes in comparison with chloro substituted ones.     

C7 and C9 carbon-rich bridges in diruthenium systems: synthesis, spectroscopic, and theoretical investigations of different oxidation States

Two methodologies of C-C bond formation to achieve organometallic complexes with 7 or 9 conjugated carbon atoms are described. A C7 annelated trans-[Cl(dppe)2Ru=C=C=C-CH=C(CH2)-C[triple bond]C-Ru(dppe)2Cl][X] (X = PF6, OTf) complex is obtained from the diyne trans-[Cl(dppe)2Ru-(C[triple bond]C)2-R] (R = H, SiMe3) in the presence of [FeCp2][PF6] or HOTf, and C7 or C9 complexes trans-[Cl(dppe)2Ru-(C[triple bond]C)n-C(CH3)=C(R1)-C(R2)=C=C=Ru(dppe)2Cl][X] (n = 1, 2; R1 = Me, Ph, R2 = H, Me; X = BF4, OTf) are formed in the presence of a polyyne trans-[Cl(dppe)2Ru-(C[triple bond]C)n-R] (n = 2, 3; R = H, SiMe3) with a ruthenium allenylidene trans-[Cl(dppe)2Ru=C=C=C(CH2R1)R2][X]. These reactions proceed under mild conditions and involve cumulenic intermediates [M+]=(C=)nCHR (n = 3, 5), including a hexapentaenylidene. A combination of chemical, electrochemical, spectroscopic (UV-vis, IR, NIR, EPR), and theoretical (DFT) techniques is used to show the influence of the nature and conformation of the bridge on the properties of the complexes and to give a picture of the electron delocalization in the reduced and oxidized states. These studies demonstrate that the C7 bridging ligand spanning the metal centers by almost 12 angstroms is implicated in both redox processes and serves as a molecular wire to convey the unpaired electron with no tendency for spin localization on one of the halves of the molecules. The reactivity of the C7 complexes toward protonation and deprotonation led to original bis(acetylides), vinylidene-allenylidene, or carbyne-vinylidene species such as trans-[Cl(dppe)2Ru[triple bond]C-CH=C(CH3)-CH=C(CH3)-HC=C=Ru(dppe)2Cl][BF4]3.     

Insertion of CO2, ketones, and aldehydes into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium

The synthesis and structures of a series of new water-soluble phosphine ligands based on 1,3,5-triaza-7-phosphaadamantane (PTA) are described. Insertion of aldehydes or ketones into the C-Li bond of 1,3,5-triaza-7-phosphaadamantan-6-yllithium (PTA-Li) resulted in the formation of a series of slightly water-soluble beta-phosphino alcohols (PTA-CRR'OH, R = C6H5, C(6)H(4)OCH(3), ferrocenyl; R' = H, C(6)H(5), C(6)H(4)OCH(3)) derived from the heterocyclic phosphine PTA. Insertion of CO(2) yielded the highly water-soluble carboxylate PTA-CO(2)Li, S(2)5 degrees approximately 800 g/L. The compounds have been fully characterized in the solid state by X-ray crystallography and in solution by multinuclear NMR spectroscopy. The addition of PTA-Li to symmetric ketones results in a racemic mixture of PTA-CR(2)OH ligands with a single resonance in the (31)P{(1)H} NMR spectrum between -95 and -97 ppm. The addition of PTA-Li to aldehydes results in a mixture of diasteromeric compounds, PTA-CHROH, with two (31)P{(1)H} NMR resonances between -100 and -106 ppm. Three (eta(6)-arene)RuCl(2)(PTA-CRR'OH) complexes of these ligands were synthesized and characterized, with the ligands binding in a kappa1 coordination mode. All the ligands and ruthenium complexes are slightly soluble in water with S25 degrees = 3.9-11.1 g/L for the PTA-CRR'OH ligands and S(25) degrees = 3.3-14.1 g/L for the (eta(6)-arene)RuCl(2)(PTA-CRR'OH) complexes.     

New palladium-catalyzed cross-coupling routes to carbon functionalized metallatricarbadecaboranes

A general method for the synthesis of cage-carbon-functionalized cyclopentadienyl iron and cyclopentadienyl ruthenium tricarbadecaboranyl complexes has been developed that employs palladium-catalyzed Sonogashira, Heck, and Stille cross-coupling reactions directed at a cage-carbon haloaryl substituent. The key Li(+)[6-(p-XC(6)H(4))-nido-5,6,9-C(3)B(7)H(9)(-)] (X = I (1), Br (2), Cl (3)) haloaryl-tricarbadecaboranyl anionic ligands were synthesized in high yields via the reaction of the arachno-4,6-C(2)B(7)H(12)(-) anion with the corresponding p-halobenzonitriles (p-XC(6)H(4)-CN). The reactions of the salts 1-3 with (η(5)-C(5)H(5))Fe(CO)(2)I and (η(5)-C(5)H(5))Ru(CH(3)CN)(3)PF(6) were then used to produce the haloaryl complexes 1-(η(5)-C(5)H(5))-2-(p-XC(6)H(4))-closo-1,2,3,4-MC(3)B(7)H(9) (M = Fe, X = I (4), Br (5), Cl (6) and M = Ru, X = I (7), Br (8), Cl (9)). The sonication-promoted Sonogashira coupling reactions of 4 with terminal alkynes catalyzed by Pd(dppf)(2)Cl(2)/CuI yielded the alkynyl-linked derivatives 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhC≡C)- (10), (CH(3)CH(2)C(O)OCH(2)C≡C)- (11), ((η(5)-C(5)H(5))Fe(η(5)-C(5)H(4)C≡C))- (12)). Heck reactions of 4 with terminal alkenes catalyzed by Pd(OAc)(2) yielded the alkene-functionalized products 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = (PhCH(2)CH═CH)- (13), (CH(3)(CH(2))(2)CH═CH)- (14)), while the Stille cross-coupling reactions of 4 with organotin compounds catalyzed by Pd(PPh(3))(2)Cl(2) afforded the complexes 1-(η(5)-C(5)H(5))-2-p-RC(6)H(4)-closo-1,2,3,4-FeC(3)B(7)H(9) (R = Ph- (15), (CH(2)═CH)- (16), (CH(2)═CHCH(2))- (17)). These reactions thus provide facile and systematic access to a wide variety of new types of functionalized metallatricarbadecaboranyl complexes with substituents needed for potential metallocene-like biomedical and/or optoelectronic applications.     

Cationic Re(V) oxo complexes with poly(pyrazolyl)borates: synthesis, characterization, and stability

Cationic Re(V) oxo compounds of the type [ReO(OSiMe3)(eta 2-B(pz)4)(L)2]X [X = Cl, L = 4-(NMe2)C5H4N (1), 1-Meimz (1-methylimidazole; 2), 1/2 dmpe (1,2-bis(dimethylphosphino)ethane; 3), py (4a); X = I, L = py (4b)] can be prepared by reacting trans-[ReO2(eta 2-B(pz)4)(L)2] with XSiMe3. In solution, cations 1-4 are reactive species, and those with unidentate nitrogen donor ligands (1, 2, and 4) rearrange into the neutral derivatives [ReO(Cl)(OSiMe3)(eta 2-B(pz)4)(L)] [L = py (5), 4-(NMe2)C5H4N (6), 1-Meimz (7)], which are also reported herein. Compounds 1-3 and 5-7 have been fully characterized by the usual spectroscopic techniques, which in some cases includes X-ray crystallographic analysis (3, 6, and 7). Compound 3 crystallizes from CH2Cl2/n-hexane as yellow crystals with one molecule of CH2Cl2 solvent, and compounds 6 and 7 crystallize from THF/n-hexane as violet and red crystals, respectively, with one molecule of THF solvent in the case of 6. Crystallographic data: 3, orthorhombic space group Pn2(1)a, a = 11.311(2) A, b = 19.135(2) A, c = 15.443(2) A, V = 3342.4(8) A3, Z = 4; 6, triclinic space group P1, a = 8.7179(11) A, b = 12.5724(8) A, c = 17.750(2) A, alpha = 70.454(7) degrees, beta = 77.935(9) degrees, gamma = 77.129(8) degrees, V = 1768.1(3) A3, Z = 2; 7, monoclinic space group P2(1)/c, a = 16.356(2) A, b = 20.384(3) A, c = 17.360(3) A, beta = 106.971(12) degrees, V = 5535.8(14) A3, Z = 8.