Synthesis and reactivity of bimetallic alkoxysilyl complexes. Crystal structure of [cyclic][Fe(CO)3{.mu.-Si(OMe)2(OMe)}(.mu.-dppm)Rh(CO)] (dppm = Ph2PCH2PPh2): a complex with a .mu.2-.eta.2-SiO bridge between iron and rhodium

Braunstein, Pierre; Knorr, Michael; Villarroya, E.; DeCian, André; Fischer, Jean

doi:10.1021/om00056a050

Cited by 43 publications

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“…Structural data reported for silyl−transition-metal complexes prepared from hydrosilanes and that include only those derivatives with “classical” M−Si, M−H, and/or Si−H bonds are summarized in Table . − …”

Section: Solid-state Structuresmentioning

confidence: 99%

“…Si(Fe,Ru,Os) bonds prepared by other methods or preceding 1980 and structurally characterized. SiFe: 2.218(2); 2.222(3); , 2.224(1); 2.2277(14); 2.230(2); 2.2330(14); 2.249(1); , 2.249(3); 2.252(3); 2.258(1); 2.260(6); 2.262(2); , 2.262(1); 2.263(1); 2.263(2), 2.264(2); 2.264(2); 2.265(1); 2.266(3); 2.267(1); 2.268(8); 2.271(4); 2.275(2); 2.278(1); 2.280(3); 2.281(4); 2.285(3); 2.286(5); 2.286(1); 2.287(2); 2.290(3); 2.294(1); 2.296(2); 2.297(3); 2.301(1); 2.303(1); 2.307(1); 2.307(2); 2.310(1); 2.322(1); 2.311(2); 2.311(3); 2.3l3(6); 2.315(2); 2.316(13); 2.322(4); 2.325(3); 2.326(3); 2.327(3); 2.328(1); 2.33(1); 2.330(2); 2.338(4); 2.339(2); 2.339(1); 2.341(2); 2.346; 2.347(1); 2.350(1); 2.354(2); 2.356; 2.356(1); 2.357(3); , 2.364(5); 2.365(2); 2.366(2); 2.366(1); 2.375(2); 2.378(1);…”

Section: Solid-state Structuresunclassified

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

1998

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Section: Solid-state Structuresmentioning

confidence: 99%

Section: Solid-state Structuresunclassified

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

1998

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“…It is known from other investigations that the PÀH bond of coordinated secondary phosphines is very reactive, notably in the case of PPh 2 H, leading readily to phosphido-bridged complexes. [13±16] Silane elimination was not observed although this is a conceivable reaction which has been observed in bimetallic Fe ± Rh [17] and Fe ± Re complexes. [18] By analogy with the dinuclear oxidative addition of molecular hydrogen across a metal ± metal bond, and in order to obey the microreversibility principle, reductive elimination of hydrogen from a dinuclear complex of the type [L n (H)M-(m-PR 2 )-M'(H)L' m ] can, in principle, occur sequentially by hydrogen migration followed by reductive elimination of H 2 from one metal center or by simultaneous elimination from the two metal centers.…”

Section: Scheme 1 Formation and Dynamic Behavior Of A H 2 -M 2 -Si-omentioning

confidence: 95%

Novel Metal-to-Metal Silyl-Migration Reactions in Heterometallic Complexes

Braunstein¹,

Knorr²,

Reinhard³

et al. 2000

Chem. Eur. J.

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An unprecedented, intramolecular metal-to-metal silyl ligand migration reaction has been discovered in a series of phosphido-bridged iron-platinum complexes and which may be triggered by an external nucleophile. Thus, reaction of solutions of [(OC)3-(R1/3Si)Fe(mu-PR2R3)Pt(1,5-COD) (1a R1 = OMe, R2 = 3 = Ph; 1b R1 = OMe, R2 = R3 = Cy; 1c R1 = Ph, R2 = R3 = Ph; 1d R1 = Ph, R2 = R3 = Cy; 1e R1 = Ph, R1 = H, R3 = Ph) in CH2Cl2 with CO rapidly afforded the corresponding complexes [(OC)4Fe(mu-PR2R3)Pt(SiR1/3)-(CO)] (2a-e) in which the silyl ligand has migrated from Fe to Pt, while two CO ligands have been ligated, one on each metal. When 1a or 1c was slowly treated with two equivalents of tBuNC at low temperature, quantitative displacement of the COD ligand was accompagnied by silyl migration from Fe to Pt and coordination of an isonitrile ligand to Fe and to Pt to give [(OC)3-(tBuNC)Fe(mu-PPh2)Pt[Si(OMe)3](CNtBu)] (3a) and [(OC)3(tBuNC)-Fe(mu-PPh2)Pt[SiPh3](CNtBu)] (3c). Reaction of 2a with one equivalent of tBuNC selectively led to substitution of the Pt-bound CO to give [(OC)4-Fe(mu-PCy2)Pt[Si(OMe)3](CNtBu)] (4b), which reacted with a second equivalent of tBuNC to give [(OC)4Fe(mu-PCy2)-Pt[Si(OMe)3](CNtBu)2] (5b) in which the metal-metal bond has been cleaved. Opening of the Fe-Pt bond was also observed upon reaction of 3a with tBuNC to give [(OC)3(tBuNC)-Fe(mu-PPh2)Pt[Si(OMe)3](CNtBu)2] (6). The silyl ligand migrates from Fe, in which it is trans to mu-PR2R3 in all the metal-metal-bonded complexes, to a position cis to the phosphido bridge on Pt. However, in 5a,b and 6 with no metal-metal bond, the Pt-bound silyl ligand is trans to the phosphido bridge. The intramolecular nature of the silyl migration, which may be formally viewed as a redox reaction, was established by a cross-over experiment consisting of the reaction of 1a and 1d with CO; this yielded exclusively 2a and 2d. The course of the silyl-migration reaction was found to depend a) on the steric properties of the -SiR1/3 ligand, and for a given mu-PR2R3 bridge (R2 = R3 = Ph), the migration rate decreases in the sequence Si(OMe)3> SiMe2Ph> SiMePh2>>SiPh3; b) on the phosphido bridge and for a given silyl ligand (R1 = OMe), the migration rate decreases in the order mu-PPh2 >> mu-PHCy; c) on the external nucleophile since reaction of 1c with two equivalents of P(OMe)3, P(OPh)3 or Ph2PCH2C(O)Ph led solely to displacement of the COD ligand with formation of 11a-c, respectively, whereas reaction with two equivalents of tBuNC gave the product of silyl migration 3c. Reaction of [(OC)3-[(MeO)3Si]Fe(mu-PPh2)Pt(PPh3)2] (7a) with tBuNC (even in slight excess) occurred stereoselectively with replacement of the PPh3 ligand trans to mu-PPh2, whereas reaction with CO led first to [(OC)3((MeO)3Si)Fe(mu-PPh2)Pt(CO)-(PPh3)] (8a), which then isomerized to the migration product [(OC)4Fe(mu-PPh2)Pt[Si(OMe)3](PPh3)] (9a). Most complexes were characterized by elemental analysis, IR and 1H, 31P, 13C, and 29Si NMR spectroscopy, and in five cases by X-ray diffraction.

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“…The X-ray structure determination of the Fe-Rh complex 25 [54] establishes the presence of a SiO bridge between the metal centres. The Rh-0 distance of 2.167 A is shorter than the Rh-O distances in ether derivatives, but it is slightly longer than the Rh-O distances in aqueous complexes.…”

mentioning

confidence: 94%

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-Fe, Si-Co AND Si-Ni BONDS

Lukevics¹,

Pudova²

2000

Main Group Metal Chemistry

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The results of the structural investigations of the group 8 metal derivatives containing the direct Si-Fe, Si-Co, Si-Ni bonds are summarized in the present review. IntroductionRecently we have published a comprehensive survey of data on the molecular structure of organosilicon compounds with Si-Si [1], Si-Ge, Si-Sn, Si-Pb, Si-Ti, Si-Zr, and Si-Hf bonds [2], as a part of the structural investigations related to the silyl substituted metal derivatives. Herein, we present a review concerning the molecular structure of iron, cobalt and nickel derivatives bearing silyl substituents at the metal atoms. Compounds with transition metal-silicon bonds have been the focus of a considerable interest and there has been remarkable progress over the last few years in the preparation of complexes containing silyl and silylene ligands. This is largely motivated by the possibility to stabilize complexes otherwise unstable, the occurrence of unusual structures, novel reactivity patterns and the construction of clusters having direct metal-metal bonds. These complexes are characterized by a very rich chemistry and have important applications in a number of catalytic processes.

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Synthesis and reactivity of bimetallic alkoxysilyl complexes. Crystal structure of [cyclic][Fe(CO)3{.mu.-Si(OMe)2(OMe)}(.mu.-dppm)Rh(CO)] (dppm = Ph2PCH2PPh2): a complex with a .mu.2-.eta.2-SiO bridge between iron and rhodium

Cited by 43 publications

References 1 publication

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

Novel Metal-to-Metal Silyl-Migration Reactions in Heterometallic Complexes

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si-Fe, Si-Co AND Si-Ni BONDS

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