Reactions of Alkyl Alkylidene Complexes with Silanes. Synthesis and Characterization of Novel Tantalum 1,1-Metallasilacyclobutadiene and Disilyl-Substituted Alkylidene Complexes

Reactions of (Me3ECH2)3ZrSi(SiMe3)3(E = C, Si) with 2,6-Dimethylphenyl Isocyanide. Preferential Isocyanide Insertion into Zr−Silyl Bonds

“…2,6-Dimethylphenyl isocyanide (Fluka) was used as received. (Me 3 ECH 2 ) 3 ZrSi(SiMe 3 ) 3 [E = C ( 1 ), Si ( 2 )] were prepared by the reactions of (Me 3 ECH 2 ) 3 ZrCl with Li(THF) 3 Si(SiMe 3 ) 3 7b. Infrared spectra were recorded on a Bio-Rad FST-60A infrared spectrometer.…”

“…Early-transition-metal silyl chemistry is becoming increasingly prominent in organometallic chemistry. , Group 4 d 0 metal silyl complexes can undergo insertion reactions 2c,k,3,4 and catalyze silane polymerizations 1g,2a,b,5 and hydrosilation of alkenes and alkynes , Our research has been focused on the chemistry of Cp-free d 0 early-transition-metal complexes, such as alkyl silyl complexes . These electronically and coordinatively unsaturated complexes present a new and unique opportunity to directly compare the relative reactivities of alkyl and silyl ligands.…”

Transition metal alkylidene complexes. Pathways in their formation and tautomerization between bis-alkylidenes and alkyl alkylidynes

“…In the presence of PMe 3 , the reactions give bisalkylidene complexes (Me 3 ECH 2 )Ta(]CHEMe 3 ) 2 (PMe 3 ) 2 (E ¼ C, 14a; Si, 14b) [29,30]. In the absence of PMe 3 , 4b in benzene-d 6 decomposes within minutes at room temperature to the bridging dimeric alkyl alkylidyne complex (Me 3 SiCH 2 ) 4 Ta(m-CSiMe 3 ) 2 (15) (Scheme 3) [28], an alkyl alkylidyne complex first reported by Wilkinson and Mowat [10].…”

“…Silicon is known to stabilize an adjacent carbon-metal bond (Scheme 16) [61]. Complexes with eCH 2 SiMe 3 and/or ]CHSiMe 3 ligands have shown unique chemistry [30,34].…”

Reactivities of d0 transition metal complexes toward oxygen: Synthetic and mechanistic studies

“…This exchange is similar to the exchange Ta(NMe 2 ) 5 (6) + (Me 2 N) 3 Ta(ONMe 2 ) 2 (8) 2 (Me 2 N) 4 TaO-NMe 2 (7) discussed earlier [12] . Reactions of both (Me 2 N) 4 Ta(SiBu t Ph 2 ) (12) The −Si(SiMe 3 ) 3 group is bulkier than the −SiBu t Ph 2 group, and it may prevent the formation of additional products in the reaction of (Me 2 N) 3 TaSi(SiMe 3 ) 3 (11) with O 2 , yielding just one product [26][27][28][29][30][31][32][33][34][35][36] . In other words, kinetic barriers may have limited the reactivities of bulkier 11 and 12.…”