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DOI: 10.1039/A801585F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1885-1892

Complexes of the (1R)-(+)-camphor azine diphosphines Z,Z-3,3′-Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PxPh2 and Z,Z-3,3′-Ph2PxC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash] C10H15PxPh2 (x = exo, n = endo) with Group 6 metal carbonyls: crystal structures of the ligands and fac-[W(CO)3(E,Z-Ph2PxC10H15[double bond, length half m-dash] N–N[double bond, length half m-dash]C10H15PxPh2)]

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Bernard L. Shaw, Nasser Iranpoor, Sarath D. Perera, Mark Thornton-Pett and Jonathan D. Vessey

Abstract

Treatment of (1R)-(+)-camphor azine with 2 mole equivalents of butyllithium, followed by chlorodiphenylphosphine, gave the azine diphosphines Z,Z-3,3′-Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PxPh2 I and Z,Z-3,3′-Ph2PxC10H15[double bond, length half m-dash] N–N[double bond, length half m-dash]C10H15PxPh2 II (x = exo, n = endo); the structures of these were determined by X-ray diffraction. On boiling an ethanol solution of the exo,exo-diphosphine II with sodium ethoxide or a propan-2-ol solution containing hydrazine hydrate and acetic acid the diphosphine isomerised to the corresponding exo,endo-diphosphine I. The corresponding diphosphine dioxides III and IV were prepared by treating I or II with H2O2, respectively. Treatment of I with [Mo(CO)4(nbd)] (nbd = norbornadiene) or with [Mo(CO)3(cht)] (cht = cyclohepta-1,3,5-triene) gave fac-[Mo(CO)3(Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PxPh2)] 1a. Treatment of I with [W(CO)4(nbd)] gave the tricarbonyltungsten(>0>) complex fac-[W(CO)3(Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PxPh2)] 1b and the analogous mer complex mer-[W(CO)3(Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PxPh2)] 2. Treatment of II with [W(CO)6] gave the mer,exo,endo tricarbonyl complex 2, and the fac,endo,endo complex fac-[W(CO)3(Ph2PnC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash]C10H15PnPh2)] 3. Treatment of II with [M(CO)4(nbd)] (M = Mo, W or Cr) gave mainly a complex of type fac-[M(CO)3(Ph2PxC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash] C10H15PxPh2)] (M = Mo 4a, W 4b or Cr 4c). The crystal structure of the tricarbonyltungsten(>0>) complex 4b was determined by X-ray diffraction and the chirality around tungsten shown to be C, i.e. clockwise. Treatment of 4b with 1 mole equivalent of bromine gave the tricarbonyltungsten(II) bromide salt [WBr(CO)3(Ph2PxC10H15[double bond, length half m-dash]N–N[double bond, length half m-dash] C10H15PxPh2)]Br 5. Infrared, proton, phosphorus-31 and some carbon-13 NMR data are given.

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