Whited Matthew T, Hofmeister Gretchen E, Hodges Connor J, Jensen Laramie T, Keyes Samuel H, Ngamnithiporn Aurapat, Janzen Daron E
Department of Chemistry, Carleton College, 1 N College St, Northfield, MN 55057, USA.
Department of Chemistry and Biochemistry, St. Catherine University, 2004 Randolph Ave., St. Paul, MN 55105, USA.
Acta Crystallogr Sect E Struct Rep Online. 2014 Sep 20;70(Pt 10):216-20. doi: 10.1107/S1600536814020534. eCollection 2014 Oct 1.
The title compounds, [Mo(C5H5)(COCH3)P(CH3)2(C6H5)(CO)2], (1), and [Mo(C5H5)(COCH3)P(C2H5)(C6H5)2)(CO)2], (2), have been prepared by phosphine-induced migratory insertion from [Mo(C5H5)(CO)3(CH3)]. Both complex mol-ecules exhibit a four-legged piano-stool geometry with trans-disposed carbonyl ligands along with Mo-P bond lengths and C-Mo-P angles that reflect the relative steric pressure of the respective phosphine ligand. The structure of compound (1) exhibits a layered arrangement parallel to (100). Within the layers mol-ecules are linked into chains along [001] by non-classical C-H⋯O inter-actions between the acetyl ligand of one mol-ecule and the phenyl and methyl phosphine substituents of another. In the structure of complex (2), a chain motif of centrosymmetrical dimers is found along [010] through C-H⋯O inter-actions.
标题化合物[Mo(C₅H₅)(COCH₃)P(CH₃)₂(C₆H₅)(CO)₂](1)和[Mo(C₅H₅)(COCH₃)P(C₂H₅)(C₆H₅)₂)(CO)₂](2)是通过膦诱导[Mo(C₅H₅)(CO)₃(CH₃)]的迁移插入反应制备的。两个配合物分子均呈现出四足钢琴凳几何构型,羰基配体呈反式排列,同时钼 - 磷键长和碳 - 钼 - 磷角度反映了相应膦配体的相对空间压力。化合物(1)的结构呈现出与(100)平行的层状排列。在层内,分子通过一个分子的乙酰基配体与另一个分子的苯基和甲基膦取代基之间的非经典C - H⋯O相互作用沿[001]连接成链。在配合物(2)的结构中,通过C - H⋯O相互作用沿[010]发现了中心对称二聚体的链状结构单元。