Issue 10, 1987

Determination of the relative signs of 2J(31P–31P) in complexes of tungsten(0) and molybdenum(0) using two-dimensional [31P–31P]-COSY-45 nuclear magnetic resonance chemical shift correlation

Abstract

Two-dimensional [31P–31P]-COSY-45 n.m.r. spectroscopy has been used to determine the magnitudes and relative signs of J(31P–31P) in three- and four-spin systems. The complexes studied are of molybdenum(0) and tungsten(0) with CO and Ph2PC([double bond, length half m-dash]CH2)PPh2(vdpp), Ph2PCH2PPh2(dppm), Ph2PCH(CH2CH3)PPh2(1,1-dppp), PEt3, or PPhEt2 as ligands. It is found that 2J(31P–31P)(cis) when the P atoms are coupled via both P–M–P and P–C–P linkages and 2J(31P–31P)(trans) are of the same sign, presumably positive, and both are of opposite sign to J(31P–31P)(cis) when the P atoms are linked via the P–M–P pathway only. This suggests a dominant positive contribution to cisoid 31P–31P coupling via the P–C–P pathway.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1987, 2401-2405

Determination of the relative signs of 2J(31P–31P) in complexes of tungsten(0) and molybdenum(0) using two-dimensional [31P–31P]-COSY-45 nuclear magnetic resonance chemical shift correlation

X. L. R. Fontaine, J. D. Kennedy, B. L. Shaw and J. M. Vila, J. Chem. Soc., Dalton Trans., 1987, 2401 DOI: 10.1039/DT9870002401

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