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Title: Titanium Imido Complexes by Displacement of -SiMe 3 and C-H Bond Activation in a Ti III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC): Titanium Imido Complexes by Displacement of -SiMe3 and C-H Bond Activation in a TiIII Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2]
  1. Department of Chemistry, University of California, Berkeley, and, Chemical Sciences Division, 94720-1460 Berkeley CA USA, Department of Chemistry, South University of Science and Technology of China, 518055 Shenzhen Guangdong China
  2. Department of Chemistry, University of California, Berkeley, and, Chemical Sciences Division, 94720-1460 Berkeley CA USA
  3. Department of Chemistry, University of California, Berkeley, and, Chemical Sciences Division, 94720-1460 Berkeley CA USA, Department of Chemistry and Chemical Biology and, The Baruch '60 Center for Biochemical Solar Energy Research, Rensselaer Polytechnic Institute, 12180 Troy NY USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1401085
Grant/Contract Number:
AC02-05CH11231; FG02-07ER15903
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2017; Journal Issue: 18; Related Information: CHORUS Timestamp: 2017-10-20 15:58:48; Journal ID: ISSN 1434-1948
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ye, Qing, Ziegler, Micah S., Lakshmi, K. V., and Tilley, T. Don. Titanium Imido Complexes by Displacement of -SiMe 3 and C-H Bond Activation in a Ti III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC): Titanium Imido Complexes by Displacement of -SiMe3 and C-H Bond Activation in a TiIII Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC. Germany: N. p., 2017. Web. doi:10.1002/ejic.201700295.
Ye, Qing, Ziegler, Micah S., Lakshmi, K. V., & Tilley, T. Don. Titanium Imido Complexes by Displacement of -SiMe 3 and C-H Bond Activation in a Ti III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC): Titanium Imido Complexes by Displacement of -SiMe3 and C-H Bond Activation in a TiIII Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC. Germany. doi:10.1002/ejic.201700295.
Ye, Qing, Ziegler, Micah S., Lakshmi, K. V., and Tilley, T. Don. Thu . "Titanium Imido Complexes by Displacement of -SiMe 3 and C-H Bond Activation in a Ti III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC): Titanium Imido Complexes by Displacement of -SiMe3 and C-H Bond Activation in a TiIII Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC". Germany. doi:10.1002/ejic.201700295.
@article{osti_1401085,
title = {Titanium Imido Complexes by Displacement of -SiMe 3 and C-H Bond Activation in a Ti III Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC): Titanium Imido Complexes by Displacement of -SiMe3 and C-H Bond Activation in a TiIII Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC},
author = {Ye, Qing and Ziegler, Micah S. and Lakshmi, K. V. and Tilley, T. Don},
abstractNote = {},
doi = {10.1002/ejic.201700295},
journal = {European Journal of Inorganic Chemistry},
number = 18,
volume = 2017,
place = {Germany},
year = {Thu May 11 00:00:00 EDT 2017},
month = {Thu May 11 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/ejic.201700295

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  • The ([eta][sup 6]-arene)Ru(H)[sub 2](SiMe[sub 3])[sub 2] arene = C[sub 6]-Me[sub 6] (1a), p-cymene (1b), C[sub 6]H[sub 6] (1c) complexes have been prepared and characterized. The complexes activate both aromatic and aliphatic C-H bonds and catalyze H/D exchange in alkylsilanes upon thermolysis in benzene-d[sub 6]. A mechanism based on oxidative-addition/reductive-elimination steps which utilizes a Ru(II)-Ru(IV) cycle is proposed to account for the C-H bond activation and H/D exchange reactions. It is further proposed that H/D exchange into sites adjacent to silicon in alkylsilanes is due to the intermediacy of an [eta][sup 2]-silene complex generated by [beta]-hydrogen elimination from the silyl group.more » 19 refs., 1 fig.« less
  • The reaction of allylmagnesium chloride with the bis(amido-phosphine) complex YCl[N-(SiMe{sub 2}CH{sub 2}PMe{sub 2}){sub 2}]{sub 2} (1) results in displacement of one of the tridentate ligands rather than simple metathesis of the chloride to generate the new complex [Y({eta}{sup 3}-C{sub 3}H{sub 5})[N-(SiMe{sub 2}CH{sub 2}PMe{sub 2}){sub 2}]]{sub 2}({mu}-Cl){sub 2}. Careful product analysis showed that the identity of the magnesium byproduct was in fact the bis(amide) derivative Mg[N(SiMe{sub 2}CH{sub 2}PMe{sub 2}){sub 2}]{sub 2}; improved procedures utilize the diallylmagnesium compound Mg(C{sub 3}H{sub 5}){sub 2}{center_dot}(dioxane), which obviates the production of MgCl{sub 2}. Attempts to introduce hydrocarbyl groups on the mono(ligand) derivative YCl{sub 2}[N(SiMe{sub 2}CH{sub 2}PMe{submore » 2}){sub 2}] by control of stoichiometry have so far failed, with the exception of the formation of the bis(allyl) derivative Y-({eta}{sup 3}-C{sub 3}H{sub 5}){sub 2}[N(SiMe{sub 2}CH{sub 2}PMe{sub 2}){sub 2}] by the reaction with Mg-(C{sub 3}H{sub 5}){sub 2}{center_dot}(dioxane); this bis(allyl) derivative acts as a catalyst precursor for the polymerization of ethylene.« less
  • Heterobimetallic complexes containing asymmetric metal-metal bonds as well as homogeneous C-H bond activation by organometallic compounds are of considerable current interest largely because of their relevance to catalysis. Although coordination of an alkene to transition metal systems is generally considered a necessary activation step in many catalytic and stoichiometric organometallic reactions, little is known about alkene C-H bond activation of precomplexed olefin substrates. In this paper the authors report the first intermolecular example of olefin C-H activation by a second, different metal system of a precomplexed {pi}-ethylene transition-metal complex and the concomitant formation of a novel alkene-bridged heterobimetallic Ir-Pt complex.
  • The reaction of Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X (X = Cl, Br) with 1 equiv of various ketenimines, R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}, leads to the niobium derivatives Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}X({eta}{sup 2}(C,N)-R{sup 1}N{double bond}C{double bond}CR{sup 2}R{sup 3}) (1, X = Cl, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 2, X = Cl, R{sup 1} = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 3, X = Br, R{sup 1} = R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 4, X = Br, R{sup 1}more » = p-CH{sub 3}-C{sub 6}H{sub 4}, R{sup 2} = R{sup 3} = C{sub 6}H{sub 5}; 5, X = Cl, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}; 6, X = Br, R{sup 1} = R{sup 2} = C{sub 6}H{sub 5}, R{sup 3} = CH{sub 3}) with the expected ketenimine C{double bond}N bonding mode. Reduction of 1 with 1 equiv of Na/Hg gives the complex Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}({eta}{sup 2}(C,N)-PhN{double bond}C{double bond}CPh{sub 2}) (9) as a paramagnetic compound. The reduction of 9 with 1 equiv of Na/Hg and the subsequent addition of a proton source (ethanol) leads to the iminoacyl compound Nb({eta}{sup 5}-C{sub 5}H{sub 4}SiMe{sub 3}){sub 2}(CRNR{sup 1}) (10, R = CH(Ph{sub 2}), R{sup 1} = Ph). The one- and two-electron reductions of 1 have been studied by cyclic voltammetry experiments. The structure of 1 was determined by single-crystal X-ray diffractometry: a = 24.4904 (14) {angstrom}, b = 11.0435 (04) {angstrom}, c = 26.6130 (15) {angstrom}, {beta} = 109.890 (5){degree}, monoclinic, space group C2/c, Z = 8, V = 6,768.4 (5) {angstrom}{sup 3}, {rho}{sub calcd} = 1.3194 g/mL, R = 0.048, R{sub w} = 0.060 based on 4,806 observed reflections. The structure contains a niobium atom bonded to two cyclopentadienyl rings in a {eta}{sup 5} fashion; the coordination of the metal is completed by a Cl atom and a {eta}{sup 2}(C,N)-bonded ketenimine ligand.« less
  • Several series of complexes of the types (MeHg(SR)) and (Hg(SR){sub 2}) have been synthesized, where the ligands are members of new classes of sterically hindered thiolates, including (triorganosilyl)methanethiols, 2-(triorganosilyl)benzenethiols, 3-(triorganosilyl)pyridine-2-thiols, and bis(2-mercaptophenyl) derivatives. Detailed {sup 1}H, {sup 13}C, and {sup 199}Hg NMR studies revealed several general trends. The {sup 199}Hg chemical shifts moved upfield in the order (MeHg(SR)) < (Hg(SCR{prime}R{double prime}R{prime}{double prime}){sub 2}) < (Hg(S-aryl){sub 2}) < (Hg(S-pyridyl){sub 2}). For the (MeHg(SR)) series of complexes, {sup 1}J(Hg-C) correlates with {delta}({sup 13}C(methyl)) and with the type of thiolate ligand. Anomalous behavior is observed for oligomeric species. There is only a limitedmore » correlation of {delta}({sup 199}Hg) with steric cone angles for a subset of the complexes. Crystal data for the complexes are reported. 86 refs., 7 figs., 11 tabs.« less