首页|Synthesis and characterization of new Rh-I complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

Synthesis and characterization of new Rh-I complexes bearing CO, PPh3 and chelating P,O- or Se,Se-ligands: Application to hydroformylation of styrene

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The complexes [Rh(CO)(PPh3){Ph2PNP(O)Ph-2-P,O}] (3), [Rh(CO)(2)(Ph2P(Se)NP(Se)Ph-2-Se,Se')] (5), and [Rh(CO)(PPh3){Ph2P (Se)NP(Se)Ph-2-Se,Se')] (6), were synthesised by stepwise reactions of CO and PPh3 with [Rh(cod){Ph2PNP(O)Ph-2-P,O)1 (2) and [Rh(cod)(Ph2P(Se)NP(Se)Ph-2-Se,Se')] (4), respectively. The complexes 3, 5 and 6 have been studied by IR, as well as H-1 and 3 1 P NMR spectroscopy. The v(CO) bands of complexes 3 and 6 appear at approximately 1960 cm(-1), indicating high electron density at the Rh-1 centre. The structure of complexes 3 and 6 has been determined by X-ray crystallography, and the P-31? NMR chemical shifts have been resolved via low temperature NMR experiments. Both complexes exhibit square planar geometry around the metal centre, with the five-membered ring of complex 3 being almost planar, and the six-membered ring of complex 6 adopting a slightly distorted boat conformation. The C-O bond of the carbonyl ligand is relatively weak in both complexes, due to strong R-back donation from the electron rich Rh-1 centre. The catalytic activity of the complexes 2, 3 and 6 in the hydroformylation of styrene has been investigated. Complexes 2 and 3 showed satisfactory catalytic properties, whereas complex 6 had effectively no catalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

PO-LigandSeSe-Ligandhemilabile ligandrhodium complexhomogeneous catalysishydroformylationRHODIUM(I) CARBONYL-COMPLEXESTRANSITION-METAL-COMPLEXESCOORDINATION CHEMISTRY1'-(DIPHENYLPHOSPHINO)FERROCENECARBOXYLIC ACIDPHOSPHINITE LIGANDSOXIDATIVE ADDITIONMETHANOLCATALYSTSPH(2)PNHP(O)PH(2)HYDROGENATION

ChatziapoStoloU KA、Vallianatou KA、GrigoropouloS A、Raptopoulou CP、Terzis A、Kostas LD、Kyritsis P、Pneumatikakis G

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Natl Hellen Res Fdn, Inst Organ & Pharmaceut Chem, GR-11635 Athens, Greece

Univ Athens, Dept Chem, Inorgan Chem Lab, Athens 15771, Greece

NCSR Demokritos, Inst Mat Sci, Aghia Paraskevi 15310, Greece

2007

Journal of Organometallic Chemistry

Journal of Organometallic Chemistry

CCREI
ISSN:0022-328X
年,卷(期):2007.692(19)