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Synthesis and Complexation Behavior of the Functionalized Tripodal Phosphanecis,cis-1,3,5-Tris(cyano)-1,3,5-tris(diphenylphosphanyl)-cyclohexane (tdppcycn)

✍ Scribed by Mayer, Hermann A. ;Stößel, Philipp ;Fawzi, Riad ;Steimann, Manfred

Publisher
Wiley (John Wiley & Sons)
Year
1995
Tongue
English
Weight
596 KB
Volume
128
Category
Article
ISSN
0009-2940

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✦ Synopsis

Phosphane ligands, tripodal I Molybdenum complexes I Iridium complexes 'The synthesis of the novel potentially bistripodal ligand ciscis-1,3,5 -tris (cy ano) -1,3,5 -tris (dipheny lp hosphany 1) cyclohexane (tdppcycn) (6) is described. Starting from the tricarboxylic acid cis,cis-1,3,5-C6Hg(COOH)3 ( l ) , which is converted stepwise into the triacid chloride CiS,CiS-1,3,5-C6Hg(Cocl)3 (2), the triphenyl ester cis,cis-1,3,5-C6Hy(COOPh)3 (3), the tricarboxamide cis,&-1 ,3,5-C6H9(CONH2)3 (4), and the tricarbonitrile cis,cis-1,3,5-c6Hy(cN), ( 5 ) , we obtained tdppcycn (6) by a-deprotonation of 5 followed by treatment with CIPPhz in good yield. Treatment of 6 with Mo(CO),(q6-C7H8) and Ir(PPh&(CO)Cl gave octahedral Mo(tdppcycn) (CO), (7) and pentacoordinate Ir(tdppcycn) (C0)Cl (B), respectively, with a facially P-coordinated tdppcycn ligand. The stereochemistry of compounds 2 -8 was established by 'H-, I3C-, 31P-NMR, and IR spectroscopy. An X-ray crystal structure analysis of complex 8 confirms the trigonal-bipyramidal ground-state structure in the solid state.

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