@article { ISI:000351442700019, title = {A New Side-on End-On Ditantalum Dinitrogen Complex and Its Reaction with BuSiH3}, journal = {Zeitschrift f{\"u}r anorganische und allgemeine Chemie}, volume = {641}, number = {1, SI}, year = {2015}, month = {JAN}, pages = {123-127}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The formation of the P-cyclohexyl dinitrogen complex, (CyPh{[}NPN]Ta)(2)(mu-eta(2):eta(1)-N-2)(mu-H)(2) ((CyPh){[}NPN] = {[}CyP(CH2SiMe2NPh)(2)], and Cy = C6H11) is described and its reaction with butylsilane (BuSiH3) explored. The reaction was monitored by multinuclear NMR spectroscopy and showed the formation of a number of intermediates. The final product is a hydride-bridged imidoamido silyated species that has the imido bridging between the two central tantalum atoms. The origin of the bridging hydrides in the product is likely to arise from the excess silane present, on the basis of labeling studies.

}, keywords = {DINITROGEN, DINUCLEAR, Hydride route, HYDROSILYLATION, tantalum}, issn = {0044-2313}, doi = {10.1002/zaac.201400167}, author = {Yeo, Alyssa and Shaver, Michael P. and Fryzuk, Michael D.} } @article {1253, title = {Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)(2)(mu-H)(4) and ([NPN]Ta)(2)(mu-eta(1):eta(2)-N-2)(mu-H)(2) (where NPN = PhP(CH2SiMe2NPh)(2))}, journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie}, volume = {83}, number = {6-7}, year = {2005}, note = {ISI Document Delivery No.: 963UVTimes Cited: 4Cited Reference Count: 29}, month = {Jun}, pages = {652-660}, type = {Article}, abstract = {Reaction of phenylacetylene with the dinuclear tetrahydride complex ([NPN]Ta)(2)(mu-H)(4) gives the product ([NPN]Ta)(2)(mu-PhCCH)(mu-H)(2) (where NPN is PhP(CH2SiMe2NPh)(2)). Activation of other terminal alkynes by ([NPN]Ta)(2)(mu-H)(4) accesses ([NPN]Ta)(2)(mu-RCCH)(mu-H)(2) (R = n-Pr, t-Bu). Crystallographic analysis of the R = Ph derivative showed it to be a bis(mu-alkylidene) bound asymmetrically to the two tantalum centres. Storage of solutions of ([NPN]Ta)(2)(mu-PhCCH)(mu-H)(2) under vacuum promotes the loss of H-2 and cleavage of the C-C bond to give a bis(mu-alkylidyne) complex, ([NPN]Ta)(2)(mu-CPh)(mu-CH). Addition of diphenylacetylene did not give the desired ([NPN]Ta)(2)(mu-CPh)(2), but rather promotes a complex decomposition of the supporting [NPN] ligands. Reaction of phenylacetylene with the dinitrogen complex ([NPN]Ta)(2)(mu-eta(1):eta(2)-N-2)(mu-H)(2) results in the dissociation of the bound dinitrogen and the formation of ([NPN]Ta)(2)(mu-PhCCH)(mu-H)(2), which is identical to that derived from the reaction with the dinuclear tetrahydride.}, keywords = {activation of small molecules, alkylidene, alkylidyne, ALKYLIDYNE COMPLEXES, ALKYNE, amidodiphosphine, BONDS, DIAMIDOPHOSPHINE COMPLEXES, DINITROGEN CLEAVAGE, DINUCLEAR, END-ON, FUNCTIONALIZATION, hydride dinitrogen, LIGAND, N-2, NIOBIUM(III), SIDE-ON, tantalum}, isbn = {0008-4042}, url = {://000231832500020}, author = {Shaver, M. P. and Johnson, S. A. and Fryzuk,Michael D.} } @article {1250, title = {Phosphine-induced ancillary ligand orthometalation at a tantalum-tantalum double bond}, journal = {Organometallics}, volume = {24}, number = {11}, year = {2005}, note = {ISI Document Delivery No.: 927XMTimes Cited: 0Cited Reference Count: 32}, month = {May}, pages = {2606-2611}, type = {Article}, abstract = {The dinuclear tantalum tetrahydride complexes ((RPh)[NPN]Ta)(2)(mu-H)(4) ([NPN] = (PhNSiMe2CH2)(2)PR; R = Ph, Cy) promote the asymmetric activation of molecular nitrogen to form ((RPh)[NPN]Ta)(2)(mu-eta(1):eta(2)-N-2)(mu-H)(2). The coordinatively unsaturated dinuclear dihydride, ((RPh)[NPN]Ta)(2)(mu-H)(2), has been proposed as the reactive intermediate, with a tantalum-tantalum double bond storing four electrons with which to reduce N-2. Efforts to trap ((CyPh)[NPN]Ta)(2)(mu-H)(2) with excess PMe3 at low temperatures promoted the formation of a green product, proposed to be (CyPh [NPN]Ta(PMe3))(2)(mu-H)(2). Attempts to isolate this product promoted the orthometalation of an ancillary ligand N-Ph ring, forming (CyPh)[NPN]Ta(mu-H)(2)[mu-N(C6H4)]Ta[PN](H)(PMe3). Addition of 1 equiv of PMe3 to ((PhPh)[NPN] Ta)(2)(mu-H)(4) immediately produced the analogous orthometalation derivative, [NPN]Ta(mu-H)(2)[mu-N(C6H4)]Ta[PN](H)(PMe3).}, keywords = {BRIDGING N-2 UNIT, C-H ACTIVATION, CLEAVAGE, CRYSTAL-STRUCTURE, DINITROGEN LIGAND, DINUCLEAR, EARLY TRANSITION-METALS, END-ON, ORGANODIMETALLIC COMPLEXES, SIDE-ON}, isbn = {0276-7333}, url = {://000229233800011}, author = {Shaver, M. P. and Fryzuk,Michael D.} } @article {4340, title = {Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2 {\textquoteright}-bis(diphenylphosphino)-1,1 {\textquoteright}-binaphthyl (binap) complexes, including structural characterisation of [(dppb)ClRu(mu-D2O)-(mu-Cl)(2)RuCl(dppb)], [(eta(2)-H-2)(dppb)Ru(m}, journal = {Inorganica Chimica Acta}, volume = {270}, number = {1-2}, year = {1998}, note = {ISI Document Delivery No.: ZD760Times Cited: 31Cited Reference Count: 57}, month = {Apr}, pages = {130-144}, type = {Article}, abstract = {{Several triply-bridged diruthenium(II)(1,4-bis(diphenylphosphino)butane) complexes were synthesised and characterised by elemental analysis, UV-Vis, NMR and IR spectroscopies, The solid-state structures of [(dppb)ClRu(mu-D2O)(mu-Cl)(2)RuCl(dppb)] (1), [(eta(2)-H-2) (dppb)Ru(mu-Cl)(3)RuCl(dppb)] (2) and [TMP][(dppb)ClRu(mu-Cl)(3)RuCl(dppb)] (3) were established by X-ray crystallographic analyses (TMP=1,1,3-trimethyl-2,3-dihydroperimidinium; dppb = Ph2P(CH2)(4)PPh2). Crystals of 1.1.5C(6)D(6), 2.1.5C(7)D(8) and 3.2Me(2)CO.2H(2)O are all monoclinic, space groups P2(1)/c, P2(1)/n and C2/c, respectively, with Z=4: a=16.8681(6)}, keywords = {ASYMMETRIC HYDROGENATION, catalytic activity, crystal structures, CRYSTAL-STRUCTURE, DEHYDROGENATION, DINUCLEAR, diphosphine complexes, GENERAL-SYNTHESIS, LIGANDS, PHOSPHINE COMPLEXES, REACTIVITY, ruthenium complexes, triply-bridged complexes}, isbn = {0020-1693}, url = {://000072720900018}, author = {Macfarlane, K. S. and Thorburn, I. S. and Cyr, P. W. and Chau, Deky and Rettig, S. J. and James, Brian R.} } @article {3204, title = {INSERTION REACTION OF DIMETHYLACETYLENEDICARBOXYLATE WITH THE HEAD-TO-TAIL ISOMER OF PT2I2(MU-PPY3)2 PPY3=TRIS(2-PYRIDYL)PHOSPHINE}, journal = {Inorganica Chimica Acta}, volume = {217}, number = {1-2}, year = {1994}, note = {ISI Document Delivery No.: NA902Times Cited: 9Cited Reference Count: 15}, month = {Mar}, pages = {209-212}, type = {Note}, abstract = {The head-to-tail (HT) isomer of Pt2I2(mu-Ppy3)2 (3), where py=2-pyridyl, is made by reaction of NaI with the chloro analogue (2), which it itself synthesized via a conproportionation reaction of a Pt(0) complex and cis-PtCl2(mu-PPY3)2 (1). Complex 1 is formed by reacting appropriate Pt(II) precursors with Ppy3. Dimethylacetylenedicarboxylate (DMAD) inserts into the Pt-Pt bond of 3 to give the A-frame species HT-Pt2I2(mu-PpY3)2(mu-DMAD) (4); the reaction is kinetically first-order in both [3] and [DMAD], and the activation parameters (DELTAH(not-equal) = 38 kJ mol-1, DELTAS(not-equal) = -138 J mol-1 K-1) are consistent with a concerted process involving a four-centre transition state. Complexes 1-4 are characterized by elemental analyses and (P{H})P-31-H-1 and (Pt{H})-Pt-195-H-1 NMR spectroscopy.}, keywords = {ALKYNE COMPLEXES, bis(diphenylphosphino)methane, COMPLEXES, DIMERS, DINUCLEAR, INSERTION REACTION, KINETICS, LIGANDS, PLATINUM COMPLEXES}, isbn = {0020-1693}, url = {://A1994NA90200032}, author = {Xie, L. Y. and James, Brian R.} }