Ditertiary(phosphines and arsines) with perfluoro-(bi-1-cycloalken-1-yl) bridging groups. Preparation and properties including a solid state structure of a tetracarbonylmolybdenum derivative

Abstract

The bi-1-cycloalken-1-yl compounds [Formula: see text] react with arsines and phosphines R2EH to yield [Formula: see text]n = 2, R2E = (CH3)2As, 1; n = 2, R2E = (C6H5)2P, 2; n = 3, R2E = (CH3)2As, 3; and [Formula: see text] Methyl diphenylphosphite affords [Formula: see text] The ditertiary phosphine 2 is photochromic in the solid state. It reacts with M(CO)6 (M = Cr, Mo, W) to give (L—L)M(CO)4. Similar compounds are obtained from the ditertiary arsines 1 and 3. The solid state structure of the Mo(CO)4 derivative of 3 has been determined from three-dimensional single crystal data. The compound crystallizes in the orthorhombic space group Pbcn with a = 16.26(1) Å, b = 11.55(1) Å, c = 13.34(1)Å, and there are four molecules in the unit cell. The coordinates of the heavy atoms were determined by vector space methods. All other atomic parameters were obtained by full matrix least-squares refinement to a final R factor of 10.1% for 715 reflections. The ligand is chelated to the molybdenum atom and the resulting seven-membered ring is considerably puckered. The As—Mo—As angle is 89.6(0.2)