Journal of Chemical Crystallography

, Volume 26, Issue 1, pp 75–79 | Cite as

PhPMe2 ligand substitution in the tetracobalt cluster Co4(CO)104-PPh)2: X-ray diffraction structure of Co4(CO)8(PPhMe2)24-PPh)2

  • William H. Watson
  • Ante Nagl
  • Ming-Jaw Don
  • Michael G. Richmond
Article

Abstract

The thermal substitution chemistry of the tetracobalt cluster Co4(CO)104-PPh)2 with the phosphine ligand PhPMe2 (2.5 equiv) has been explored and found to afford the bis(phosphine)-substituted cluster Co4(CO)8(PPhMe2)24-PPh)2 as the major reaction product. The regiochemistry and stereoselectivity exhibited by the two phosphine ligands in Co4(CO)8(PPhMe2)24-PPh)2 have been unambiguously established by X-diffraction analysis as having a 1,3-cis orientation. Co4(CO)8(PPhMe2)24-PPh)2 crystallizes in the monoclinic space group P21/n,a=10.314(1) Å,b=18.051(3) Å,c=21.313(2) Å, β=90.10(1)°,V=3968.0(8) Å3,Z=4,dcalc=1.590 g cm−3;R=0.051,Rw=0.042 for 4987 observed reflections withI>3σ(I). Generalizations concerning the stereochemical disposition of two P-ligands about the Co4(CO)8P24-PPh)2 (where P=phosphine or phosphite) polyhedron are discussed with respect to the cone angle of the P-ligand and its steric interactions with the capping phenylphosphinidene group.

Key Words

Tetracobalt cluster phosphine ligand regiochemistry 

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Copyright information

© Plenum Publishing Corporation 1996

Authors and Affiliations

  • William H. Watson
    • 1
  • Ante Nagl
    • 1
  • Ming-Jaw Don
    • 2
  • Michael G. Richmond
    • 2
  1. 1.Department of ChemistryTexas Christian UniversityFort Worth
  2. 2.Center for Organometallic Research and Education, Department of ChemistryUniversity of North TexasDenton

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