DUTTA , D K and WOOLLINS , J D and SLAWIN , A M Z and KONWAR , D and SHARMA , M and BHATTACHARYYA , P and AUCOTT , S M (2006) Rhodium(I) carbonyl complexes of mono selenium functionalized enylphosphino)methane and Bis(di- phenylphosphino)amine chelating ligands and their catalytic carbonylation activity. J Organometallic Chemistry, 69. pp. 1229-1234.

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The chelate complexes of the types [Rh(CO)Cl(Ph2PCH2P(Se)Ph2)] (1) and [Rh(CO)Cl(Ph2PN(CH3)P(Se)Ph2)] (2) have been synthesized and characterized by IR and NMR spectroscopy. The lower shift of the m(P–Se) bands and downfield shift of the 31P– { 1H}NMR signals for both P(III) and P(V) atoms in 1 and 2 compared to the corresponding free ligands indicate chelate formation through selenium donor. 1 and 2 show terminalm(CO) bands at 1977 and 1981cm 1, respectively, suggesting high electron density at themetalcenter.Themolecularstructureof2hasbeendeterminedbysingle-crystalX-raydiffraction.Therhodiumatomisatthecenter ofasquareplanargeometryhavingthephosphorusandseleniumatomsofthechelatingligandatcis-position,onecarbonylgrouptransto selenium and one chlorine atom trans- to phosphorus atom. 1 and 2 undergo oxidative addition (OA) reaction with CH 3I to produce acyl complexes [Rh(COCH3)ClI(Ph2PCH2P(Se)Ph2)] (3) and [Rh(COCH3)ClI(Ph2PN(CH3)P(Se)Ph2)] (4), respectively. The kinetics of the OAreactionsrevealthat1undergoesfasterreactionbyabout4.5timesthan2.Thecatalyticactivityof1and2incarbonylationofmethanol was higher than that of the well known species [Rh(CO) 2I2]  and 2 shows higher catalytic activity compared to 1.  2005 Elsevier B.V. All rights reserved. Keywords: Rhodium(I) carbonyl complexes; Bis(diphenylphosphino)methane selenide; Bis(diphenylphosphino)amine selenide; Oxidative addition; Carbonylation

Item Type: Article
Subjects: Chemistry > Material Science
Depositing User: Dr. PK Barooah
Date Deposited: 04 Jan 2012 09:29
Last Modified: 04 Jan 2012 09:29
URI: http://neist.csircentral.net/id/eprint/283

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