Hydroboration of (&mgr;-H)(2)Os(3)(CO)(10): Formation of the Borylidyne Cluster (&mgr;-H)(2)Os(3)(CO)(9)(&mgr;-H)(2)BH. An Improved Synthesis of (&mgr;-H)(3)Os(3)(CO)(9)(&mgr;(3)-BCO).
At room temperature, the reaction of (&mgr;-H)(2)Os(3)(CO)(10) with BH(3)S(CH(3))(2) produces the new borylidyne cluster (&mgr;-H)(2)Os(3)(CO)(9)(&mgr;-H)(2)BH, a methylidyne cluster analog. At 65 degrees C the previously reported ketenylidene cluster analog (&mgr;-H)(3)Os(3)(CO)(9)(&mgr;(3)-BCO) is formed. The complex (&mgr;-H)(2)Os(3)(CO)(9)(&mgr;-H)(2)BH was characterized by (1)H NMR, (11)B NMR, and infrared spectroscopies as well as mass spectrometry. Its molecular structure was determined from a single-crystal X-ray analysis. The molecule is of approximate C(s)() symmetry. It consists of a tetrahedral Os(3)B core with a terminal B-H bond, two Os-H-B, hydrogen bridge bonds, and three Os(CO)(3) units. A similar structure has been proposed for one of the isomers of a ruthenium analog, (&mgr;-H)(2)Ru(3)(CO)(9)(&mgr;-H)(2)BH, but it differs from the related iron complex (&mgr;-H)Fe(3)(CO)(9)(&mgr;-H)(3)BH which has three Fe-H-B bridge bonds. Crystal data for (&mgr;-H)(2)Os(3)(CO)(9)(&mgr;-H)(2)BH: triclinic space group P&onemacr;, a = 9.501(4) Å, b = 9.525(4) Å, c = 10.070(2) Å, alpha = 87.72(3) beta = 88.32(3) degrees, gamma = 61.45(3) degrees, Z = 2.
Chung
Jang-Hoon
JH
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210.
Boyd
Edwin P.
EP
Liu
Jianping
J
Shore
Sheldon G.
SG