Hydrosilylation of Carbonyl Compounds with Hydrosilyliron Complexes Catalyzed by Cationic Silyleneiron Complexes

Muraoka, Takako; Shimizu, Yuusaku; Kobayashi, Hideki; Ueno, Keiji

doi:10.1021/om100398u

Cited by 14 publications

(5 citation statements)

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“…58 Another simple substitution was reported for Cp(OC) 2 FeSiMe 2 Cl with i PrONa, which gave a -SiMe 2 O i Pr substituent. 239 241 and Cp*-(OC)HRuSi(H)C(SiMe 3 ) 3 reacts with acetone, Me 2 CO, as well as HPhCO to incorporate an -OCHMe 2 and a OCH 2 Ph group at the Si center of the complex. 240 Hydrogenation of the RuSiPh 2 unit in 4-18 gave 4-17.…”

Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 96%

“…The reverse type of reaction, reduction of Si–Cl by LiAlH 4 (and LiAlD 4 ), was reported for formation of the inorganic ethylenes, H 2 Si-ElH 2 (El = Ge, Sn, coordinated to W(CO) 5 ) from IPr·SiCl 2 ElCl 2 ·W(CO) 5 reported by Rivard and co-workers . Another simple substitution was reported for Cp(OC) 2 FeSiMe 2 Cl with i PrONa, which gave a -SiMe 2 O i Pr substituent . Si–H bonds can also undergo addition to multiple bonds, including CC and CO.…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“…Hydride abstraction from a coordinated silicon substituent has provided a cationic silylene complex, [Cp(OC) 2 FeSiR 2 ·NCCD 3 ] + [B(C 6 F 5 ) 4 ] − (R = p -tolyl, Me (generated in situ before reaction with acetone, PhCHO, and acetone/PPh 3 )) . A similar type of reaction occurs with Cp*(P i Pr 3 )Ru(H) 2 (SiHMesOTf) and [Et 3 Si][B(C 6 F 5 ) 4 ] (OTf removed preferentially) to give the cationic silylene, [Cp*(P i Pr 3 )Ru(H) 2 (SiHMes)][B(C 6 F 5 ) 4 ], which was isolated and characterized .…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“…127 Hydride abstraction from a coordinated silicon substituent has provided a cationic silylene complex, [Cp(OC) 2 FeSiR 2 • NCCD 3 ] + [B(C 6 F 5 ) 4 ] − (R = p-tolyl, Me (generated in situ before reaction with acetone, PhCHO, and acetone/PPh 3 )). 239 A similar type of reaction occurs with Cp*(P i Pr 3 )Ru-(H) 2 (SiHMesOTf) and [Et 3 Si][B(C 6 F 5 ) 4 ] (OTf removed preferentially) to give the cationic silylene, [Cp*(P i Pr 3 )Ru-(H) 2 (SiHMes)][B(C 6 F 5 ) 4 ], which was isolated and characterized. 91 Another example of removal of OTf 241 The focus in this section has been on reactions where the outcome is predictable, but there are certainly other reactions that have been performed involving a silyl substituent or a metal-silylene where it is more difficult to predict the outcome: as an example, the thermolysis reaction reported for 5-80b.…”

Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 96%

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Section: Formation Of Silylene Complexes From Si(iv) Precursors and R...mentioning

confidence: 99%

See 2 more Smart Citations

Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…In this regard, noteworthy efforts have been devoted to the development of efficient and selective reaction of hydrosilanes to olefins employing a wide variety of transition metals [3][4][5][6][7][8][9][10]. Since iron is much less expensive and environmentally friendly compared to other transition metals like Rh, Pt and Ru [11], iron-based catalysts for hydrosilylation have received considerable interests [12][13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%