Complexes of 3,3′‐Oxybis[(diphenylphosphino)methylbenzene] with Ni(II), Pd(II), Pt(II), Rh(I), and Ag(I). How Important is Backbone Rigidity in the Formation of trans‐Spanning Bidenatate Chelates??

The bidentate diphosphine ligand, 3,3′‐oxybis[(dipenylphosphino)methylbenzene] (1) forms monomeric, trans‐square‐planar complexes MX2(1) (M = Ni, Pd, Pt; X = Cl−, Br− I−, and, in part, N , NCS−, CN−, NO ) as well as Pt(H)Cl(1), Pt(H)Br(1), and RhCl(CO)(1). Polymeric species have been observed with substitutionally inert metal centres: trans‐[PtCl2(1)]2 and cis‐[PtCl2(1)]n (mean value of n ≈ 4–5) 31P‐NMR, and selected IR and UV/VIS parameters are reported. Ligand 1 shows a marked preference for trans‐spanning and monomeric chelate formation, despite its various degrees of freedom of internal rotation in the lignad backbone. The readily available ligand 1 as well as analogues with other donor atoms, therefore, appear useful in most potential applications of trans‐spanning chelate ligands. The crystal structure of AgCl(1)·0.5 (CH3)2CO·0.39 C6H12 (space group C2/c,a = 21.02 Å, b = 14.57 Å, c = 24.79 Å, β = 99.77°, V = 7531.4 Å3, Z = 8) confirms the presence of three‐coordinate Ag(I), with a coordination intermediate between a trigonal‐planar and a T‐shaped geometry (P‐Ag‐P = 145.61(8)°).