Preparation and structure of a disilarhodacycle, fac-[Rh(SiMe2CH2CH2SiMe2)H(PMe3)3]

Osakada, Kohtaro; Hataya, Kouji; Nakamura, Yoshiyuki; Tanaka, Masako; Yamamoto, Takakazu

doi:10.1039/c39930000576

Cited by 18 publications

(6 citation statements)

References 9 publications

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“…When complex 4 − 244 was heated, intramolecular oxidative addition of the remaining Si−H bond occurred to give complex 4 − 245 . The synthesis of [ fac -(Me 3 P) 3 (H)Rh(SiMe 2 CH 2 CH 2 SiMe 2 )] ( 4 − 242 , X-ray) was reported from reaction of (Me 3 P) 3 Rh(SPh) and an excess of the bifunctional silane, HMe 2 SiCH 2 CH 2 SiMe 2 H (a 1:1 ratio of reagents does not give complex 4 − 242 ) at room temperature. Cyclometalladisiloxanes with the general formula, OC(Ph 3 P) 2 HIr[SiMe(R)OSiMe(R)] (where R = Ph or CH 2 Ph) were prepared by the oxidative addition of Si−H bonds in siloxanes to (Ph 3 P) 2 Ir(CO)Cl (see entry 4 − 266 253 ).…”

Section: Tertiary Silanesmentioning

confidence: 99%

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

1998

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Section: Tertiary Silanesmentioning

confidence: 99%

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

1998

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“…2,5-Disila-1-metallacyclopentanes − have attracted attention owing to their unique chemical properties and the important roles they play as an intermediate of transition metal complex catalyzed hydrosilylation and bis-silylation of unsaturated compounds. , Most of these complexes were prepared by the oxidative addition of two Si−H bonds of 1,2-bis(silyl)alkanes, HSiR 2 CH 2 CH 2 SiR 2 H, to low-valent transition metal complexes. On the other hand, the reactions of alkene and alkyne with M(SiX 3 ) 2 (PR 3 ) 2 (M = Pd, Pt; X = Me, Ph, F) lead to the formation of their 1,2-disilylation products, , which are closely related to the mechanism of bis-silylation of alkene, allene, and alkyne catalyzed by transition metal complexes. − A similar reaction of alkene or allene with Pt complexes having diorganosilyl ligands would lead to the formation of 1,2-bis(silyl)alkane or 2,5-disila-1-metallacyclopentane as its double oxidative addition product.…”

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confidence: 99%

Four-, Five-, and Six-Membered Silaplatinacycles Obtained from the Reaction of an Arylallene with Pt(SiHPh₂)₂(PMe₃)₂

2001

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The reaction of (4-fluorophenyl)allene with Pt(SiHPh 2 ) 2 (PMe 3 ) 2 gives 2-sila-1-platinacyclobutane, 2,5-disila-1-platinacyclopentane, or 4-sila-1-platinacyclohexane, depending on the reaction conditions. All these complexes were characterized by X-ray crystallography and NMR spectroscopy.2,5-Disila-1-metallacyclopentanes 1-10 have attracted attention owing to their unique chemical properties and the important roles they play as an intermediate of transition metal complex catalyzed hydrosilylation and bis-silylation of unsaturated compounds. 3,8 Most of these complexes were prepared by the oxidative addition of two Si-H bonds of 1,2-bis(silyl)alkanes, HSiR 2 CH 2 CH 2 -SiR 2 H, to low-valent transition metal complexes. On the other hand, the reactions of alkene and alkyne with M(SiX 3 ) 2 (PR 3 ) 2 (M ) Pd, Pt; X ) Me, Ph, F) lead to the formation of their 1,2-disilylation products, 11,12 which are closely related to the mechanism of bis-silylation of alkene, allene, and alkyne catalyzed by transition metal complexes. [13][14][15] A similar reaction of alkene or allene with Pt complexes having diorganosilyl ligands would lead to the formation of 1,2-bis(silyl)alkane or 2,5-disila-1-metallacyclopentane as its double oxidative addition product. Actually, Pt(SiHPh 2 ) 2 (PMe 2 Ph) 2 was reported to react with acetylene to afford Pt(SiPh 2 -CHdCH-SiPh 2 )(PMe 2 Ph) 2 . 16 In this paper we report that the reaction of an arylallene with a platinum complex with diphenylsilyl ligands gives not only a new disilaplatinacyclopentane but also four-or five-membered silaplatinacycles depending on the conditions.(4-Fluorophenyl)allene reacts with an equimolar amount of Pt(SiHPh 2 ) 2 (PMe 3 ) 2 17 at room temperature to produce Pt(SiPh 2 C(dCHC 6 H 4 F-4)CH 2 )(PMe 3 ) 2 (1),

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“…Cleavage of a stable Si−O bond should occur during the reaction, and a mechanism involving an intermediate silylene complex was proposed. Oxidative addition of dmseH 2 to the Rh(I) thiolato complex [Rh(SPh)(PMe 3 ) 3 ] produces a disilarhodacycle with a hydride ligand, fac -[RhH(SiMe 2 CH 2 CH 2 SiMe 2 )(PMe 3 ) 3 ] ( 8 ) …”

Section: Disilylated and Digermylated Metallacyclesmentioning

confidence: 99%

Sila- and Germametallacycles of Late Transition Metals

Tanabe

Osakada

2010

Organometallics

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This article reviews recent advances in late-transition-metal complexes with chelating Si and Ge ligands. Compounds with two Si-H bonds, such as bis(silyl)alkanes, bis(silyl)arenes, and tetramethyldisiloxanes, react with Re, Rh, Ir, Pd, and Pt complexes to form disilametallacycles with five-or six-membered chelate rings. Four-and five-membered disilacycloalkanes and disilanyldiylcarboranes undergo Si-Si bond cleavage promoted by Pd(0) and Pt(0) complexes to produce the corresponding disilametallacycles. High reactivity of the Si-Si bond toward oxidative addition facilitates the above ring enlargement, even for compounds with stable five-membered rings. Platinum complexes with a η 2 -silene ligand react with small molecules having electronegative atoms, such as O 2 and NH 3 , to produce metallacycles formed via addition of the electronegative atom to the Si-Si bond. The above disilametallacycles undergo insertion of alkynes and carbonyl compounds into the M-Si bonds of the disilametallacycles. The persilyl metallacycle [ À Pt(SiPh 2 SiPh 2 SiPh 2 À SiPh 2 )(PPh 3 ) 2 ] is obtained by the double oxidative addition of tetrakis-(diphenylsilane) with two Si-H groups and via a metathesis reaction of its dilithio derivative with [PtCl 2 (PPh 3 ) 2 ]. Reactions of H 2 GeAr 2 with Pd(II) and Pt(II) complexes having diphenylgermyl ligands yield the tetragerampalladacyclopentane and its Pt analogue. Trigermaplatinacyclobutane reacts with Ph 2 GeH 2 to produce the tetragermaplatinacyclopentane via formal insertion of GePh 2 into a Pt-Ge bond. C versus Si or Ge MetallacyclesThe chemistry of metallacycles 1 has been a major area of organometallic chemistry because of their role as key intermediates in the metathesis 2 and oligomerization 3 of alkenes catalyzed by transition-metal complexes. Five-and six-membered metallacycles are common, and they are stabilized kinetically in many cases. Their M-C bonds undergo various reactions such as insertion of small molecules, reductive elimination of cycloalkanes, and β-hydrogen elimination, but the reactions occur more slowly than for the usual alkyl complexes due to ring strain of the intermediates or the products. Metallacyclobutanes of Mo, W, and Ru with a four-membered-ring structure are known as the actual intermediates of olefin metathesis catalyzed by the transition-metal complexes. 4 Silyl and germyl complexes of late transition metals exhibit different reactivity from the alkyl metal complexes. For example, they prefer R-hydrogen elimination rather than β-hydrogen elimination, which is common as a decomposition pathway of the alkyl complexes. Chemical properties of the metallacycles, having Si or Ge as the coordinating atoms, are expected to be unique, being cyclic versions of the silyl and germyl complexes. Many research groups have investigated the preparation, structures, and chemical properties of such sila-or germametallacycles. Pd and Pt, in particular, are employed as the major elements among late transition metals, probably because the σ-bonds between Si or Ge and thes...

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Preparation and structure of a disilarhodacycle, fac-[Rh(SiMe2CH2CH2SiMe2)H(PMe3)3]

Cited by 18 publications

References 9 publications

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Four-, Five-, and Six-Membered Silaplatinacycles Obtained from the Reaction of an Arylallene with Pt(SiHPh₂)₂(PMe₃)₂

Sila- and Germametallacycles of Late Transition Metals

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Preparation and structure of a disilarhodacycle, fac-[Rh(SiMe2CH2CH2SiMe2)H(PMe3)3]

Cited by 18 publications

References 9 publications

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Four-, Five-, and Six-Membered Silaplatinacycles Obtained from the Reaction of an Arylallene with Pt(SiHPh2)2(PMe3)2

Sila- and Germametallacycles of Late Transition Metals

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Product

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Four-, Five-, and Six-Membered Silaplatinacycles Obtained from the Reaction of an Arylallene with Pt(SiHPh₂)₂(PMe₃)₂