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Synthesis and Reactivity of Phosphine-substituted Hydrido Silyl Complexes mer-> (n=1 or 4), mer- and mer->. Synthesis of Bimetallic Complexes and Crystal Structure of mer-

DOI: 10.1039/DT9910001507

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1507 - 1514 (1991)

Update date:2022-08-02

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Authors:

Braunstein, PierreBraunstein, Pierre

Knorr, MichaelKnorr, Michael

Schubert, UlrichSchubert, Ulrich

Lanfranchi, MaurizioLanfranchi, Maurizio

Tiripicchio, AntonioTiripicchio, Antonio

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Article abstract of DOI:10.1039/DT9910001507

Phosphine-subsituted hydrido silyl complexes (L=phosphine) have been prepared by carbonyl substitution in cis-.The reaction of cis-(CO)4> 1a with Ph2PCH2PPh2 (dppm) in a 1:1 ratio afforded mer-(CO)3(dppm-P)> 2a; mer-(CO)3(dppm-P)> 2b was obtained similarly.The reaction of FeH(SiPh3)(CO)4> with Ph2P(CH2)4PPh2 (dppb) afforded mer- 3a and that of 1a with vinylidenebis(diphenylphosphine) (vdpp) afforded under analogous conditions the chelated complex cis-Si(OMe)3>(CO)2(vdpp-PP')> 3c.Reaction of 1a with the functional phosphine Ph2PCH2C(O)Ph yielded mer-(CO)3> 4 and with PPh2H, mer-(CO)3(PPh2H)> 5 was obtained.The anionic complexes K 6a (R=OMe, X=CH2PPh2), 6b (R=OEt, X=CH2PPh2), 6c and 6d were generated from the corresponding hydrido complexes by deprotonation with excess of KH in tetrahydrofuran (thf).They were used to prepare metal-metal bonded heterobinuclear complexes mer-(CO)3> 7b (M=Cu, L=PPh3), 7c (M=Cu, L=MeCN), 8a (M=Ag, L=AsPh3), 8b (M=Ag, L=PPh3) and 10 (M=Au, L=PPh3).Complex 8a dissociates AsPh3 in solution with formation of mer-(CO)3> 9, which contains an unusual alkoxysilyl bridge resulting in a AgFeSiO four-membered ring.This very labile complex was also obtained from the reaction of 6a with NO3.For comparative purposes, we also prepared mer-<(Ph3P)AuFe(CO)3(PPh3)> 11.All complexes were characterized by elemental analysis and spectroscopic (IR and 1H and 31P-<1H> NMR) methods.The crystal structure of compound 7b has been determined by X-ray diffraction: monoclinic, space group P21/C, with a=11.542(5), b=18.567(7), c=21.830(7) Angstroem, β=94.67(2) deg and Z=4.The copper atom is trigonally co-ordinated by two phosphorus atoms from the dppm and PPh3 ligands and by the Fe atom .The Fe atom is in an octahedral arrangement determined by three carbon atoms from carbonyl groups, a phosphorous atom of the bridging dppm ligand and by the Si atom of the Si(OMe)3 group.

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Product name:K{Fe(SiPh3)(CO)3(bis(diphenylphosphino)butane)}

Cas No:135745-71-0

135745-71-0

R&D Labs maybe for 135745-71-0

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