Download Comprehensive Organometallic Chemistry III, Volume 5 : by Klaus Theopold PDF

By Klaus Theopold

This quantity stories the practise, homes, reactions and unique purposes of crew five to 7 organometallic compounds. each one bankruptcy examines the compounds shaped among Vanadium, Niobium, Tantalum, Chromium, Molybdenum, Tungsten, Manganese, Technetium and Rhenium and particular ligands. It presents a transparent and entire assessment of advancements in view that 1993 and makes an attempt to foretell traits within the box over the following ten years. Like its predecessors, COMC (1982) and COMC-II (1995), this new paintings is the fundamental reference textual content for any chemist or technologist who must use or follow organometallic compounds.

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Analogous dinitrogen fixation is also achieved in the low temperature reaction of VCl3(THF)3 with 3 equiv. of neopentyllithium in diethyl ether under dinitrogen. 116 Relevant structural parameters for Np3V("-N2)VNp3 are listed in Table 6, and compare well with Mes derivatives, the V–Np bond is among the shortest reported for Table 6 Structural parameters for alkyl-dinitrogen vanadium complexes Complex ˚ V–C (A) ˚ V–N (A) ˚ NTN (A) V–N–N ( ) References {[Mes3V("-N2)VMes3][K(digly)3]} {[K(digly)3("-Mes)2(Mes)V]2("-N2)} {[Mes3V("-N2)VMes3][Na(digly)2]2} {[Mes3V("-N2)("-Na)VMes3][Na(digly)2]} Np3V("-N2)VNp3 av.

150(3) A. 136 Amidinates have also been found to be suitable ancillary ligands for electron-deficient vanadium(III) hydrocarbyl species. 137,138 3-Allyl congeners have been prepared similarly. These neutral alkyl systems are thermally robust and catalyze slowly the oligomerization of ethene to linear alkenes without the need of added co-catalyst. Treatment of mono-(-diiminato) precursor [ArNC(R1)CHC(R1)NAr]VCl2(THF)n [Ar ¼ Ph, 2,6-Pri2-C6H3, 2,4,6Me3-C6H2; R1 ¼ Me, But; n ¼ 0 or 2 with R1 ¼ Ph] with alkyllithium reagents affords surprisingly stable NCPh2 *Si CH3 *Si *Si R Cl *Si N V *Si N THF *Si Si* N x ix 25 *Si *Si i N V *Si N NCPh *Si Si* N V *Si N Cl *Si Si* iii ii R *Si N V *Si N Py *Si Si* N V *Si N CH3 *Si Si* [Li(TMEDA)2]+ 38 v iv But *Si R vii 36 *Si Si Si* H C 2 N V *Si Si* N C V H2 Si* N Si Si* *Si *Si N Si* H3C N Si * V O V *Si N CH3 *Si N Si* Si* ix CH3 Xyl viii R = Ph 35b But N V *Si N *Si t Si* Bu vi N V *Si N THF *Si Si* R = Me 35a CH3 N *Si R N N V *Si N N *Si Si* N V *Si N O *Si Si* NXyl 37 26 [Si* = SiMe3]; i, 1/2 MgR2 [R = CH3, Ph]; ii, 2LiMe, 2TMEDA; iii, Py; iv, CuCl; v, PhCN [R = Ph]; vi, 3CNBut [R = CH3]; vii, 3CNXyl [R = CH3]; viii, 1 styrene oxide [R = CH3, Ph]; ix, 1/2 styrene oxide [R = CH3]; x, Δ, –RH [R = CH3, Ph] Scheme 14 17 18 Vanadium Organometallics R2 R2 1 R1N R1N NR V Cl 1 NR RMgBr R1N THF, –78 °C R1N R1,R2 NR1 V R R Me 1 NR R2 (Pri,But) (SiMe3,Ph) (SiMe3,C6F5) 34% 61% 52% 66% Et R2 68% 72% allyl 39 Scheme 15 R1 R1 Ar N N R1 V Cl (THF)n Cl N 2RLi n [R = Me, Bu , Np] N R1 Ar Ph N V Cl R N Ph RLi [R = Me, CH2SiMe3] R1 Ar AgOTf V R R [R = Np] N R1 42 Ar Ph N RLi N V R R HBArF4 / Et2O [R = Me] Ph 40 Ar N 41 V Np OTf Ar 44 Ph N THF V OEt2 [BArF4] Me N Ph 43 (Ar, R1, n) = (2,4,6-Me3-C6H2, Me, 0), (2,6-Pri3-C6H3, Me, 0), (Ph, Me, 0),(2,4,6-Me3-C6H2, But, 2) Scheme 16 dialkylvanadium(III) complexes [ArNC(R1)CHC(R1)NAr]VR2 41 and 42 (R ¼ Me,139–141 Bun,139 CH2SiMe3,140,141 CH2But142) as well as monoalkyl complex 40 (see Scheme 16).

The ethylidyne fragment is unsymmetrically coordinated ˚ which indicates two non-equivalent V–C bonds (double vs. single). 10) of tetravalent and pentavalent vanadium has been examined. 163 At 423 K, neopentane adds to the VTN bond of the imido derivative via C–H addition. 164,165 It undergoes surprisingly clean thermal (58  C) -H elimination of SiMe4 to generate the supported alkylidene (USiO)2V(TCHSiMe3). When exposed to excess of styrene at room temperature, this alkylidene species affords trimethylvinylsilane by metathetical exchange.

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