Multimode coordination chemistry of [R2P(X)CHnP(Y)R'2](2-n)- ligands (X, Y = O, S, Se; n = 1, 2). Synthesis and phosphorus-31 NMR spectroscopy of platinum complexes

Author
Berry, David E.
Browning, Jane
Dixon, Keith R.
Hilts, Robert
Pidcock, Alan
Faculty Advisor
Date
1992
Keywords
Abstract (summary)
Reactions of the bis(phosphine chalcogenides) CH2|P(X)R2l|P(Y)R'2l (X, Y = O, S, Se) and their derived anions [CH|P-(X)R2)lP(Y)R'2l]" with chloroplatinum complexes PtCl42", [Pt2Cl4(PEt3)2], or [Pt2Cl2(PEt3)4]2+ result in a wide variety of coordination complexes. For example, when R = R' = Ph and X = Y = S, the following are all accessible in high yield: [PtCl(PEt3){CH2(P(S)Ph2)2-S^|]+, [PtCl(PEt3)iCH(P(S)Ph2)2-C,S|], [PtCl(PEt3)|CH(P(S)Ph2)2-S^|], [Pt(PEt3)2|CH2(P(S)-Ph2)2)-5^i]2+, [Pt(PEt3)2(CH(P(S)Ph2)2-C,S|]+, [PtCl2lCH2(P(S)Ph2)2-S^l], [Pt|CH2(P(S)Ph2)2-.S„S|2]2+, and [Pt(CH(P-(S)R2)2-C^|2]· A more limited range of complexes is also reported for X = Y = O, X = Y = Se, and X = O, Y = S. In general, the ligands exhibit at least five different coordination modes: (i) Bidentate X,Y coordination of neutral ligands; (ii) bidentate X,Y coordination of the anionic ligands; (iii) bidentate C,X coordination of the anions in a strained four-membered ring; (iv) monodentate C coordination of the anions; (v) complex C,S bridging mode involving a dianionic ligand and two metal centers. Interconversion reactions and characteristic 31P NMR spectroscopy are described for all of the coordination modes, including dynamic NMR studies of the C,X modes. These last modes all exhibit some degree of fluxional behavior, involving an exchange of coordinated and noncoordinated P=X groups in essentially a classic “bimolecular” substitution reaction, except that the incoming ligand is actually part of one of the existing ligands.
Publication Information
David E. Berry, Jane Browning, Keith R. Dixon, Robert W. Hilts, & Alan Pidcock (1992). Multimode coordination chemistry of [R2P(X)CHnP(Y)R'2](2-n)- ligands (X, Y = O, S, Se; n = 1, 2). Synthesis and phosphorus-31 NMR spectroscopy of platinum complexes. Inorganic Chemistry, 31(8), DOI: 10.1021/ic00034a031
DOI
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Item Type
Article
Language
English
Rights
All Rights Reserved