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??

Abstract

The bidentate diphosphine ligdnd, 3,3'-oxybis[(dipenylphosphino)methylbenzene] (1) forms monomeric, truns-square-planar complexes MX2(1) (M = Ni, Pd, Pt; X = CI-., Br-, I-, and, in

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

“…The Ag atom is three-coordinate with the AgP 2 Cl central coordination unit in a planar configuration. The arrangement of the donor atoms is intermediate between a trigonal planar and T-shaped geometry with P(1)−Ag−P(2) = 145.61(8)° for the more flexible pop ligand and 140.7(1)° for the more rigid L1a ligand . Thus, the less rigid pop ligand prefers larger P(1)−Ag−P(2) bond angles than the flexible L1a ligand.…”

“…To determine the effect of the rigidity of the preformed span, Kapoor and co-workers synthesized the Ag(pop)Cl complex for comparison with Ag(L1a)Cl . The molecular structure of Ag(pop)Cl closely resembles that of Ag(L1a)Cl.…”

Coordination complexes of silver(I) with tertiary phosphine and related ligands

“…Mononuclear complexes of Type 5 (Scheme 8) have been obtained for the ligands 2,11-bis(di-R-phosphinomethyl)benzo(c)phenanthrene (R = Ph, X = Cl, SnCl 3 [135]; R = t Bu, X = Cl, Br, ClO 4 [136], Et [137]), 3,3 -oxybis[(diphenylphosphino)methyl]benzene [138], bis(diphenylphosphanyl)-O-carborane [139] and R-[(4-MeC 6 H 4 ) 2 P(C 10 H 6 ) 2 ] 2 [(R)-Tol-Binap] [140].…”

Trans-chelating diphosphines, the elusive ligands!

“…Many trans-complexes of ligand 14 have been synthesized as Ni14X 2 (X = Cl, I, NCS, CN), Pd14X 2 (X = Cl, Br, I, ONO, N 3 ), Pt14X 2 (X = Br, I, Cl), Pt14HCl, Pt14HBr, Ag14Cl or Rh14(CO)Cl and fully characterized by spectroscopic techniques [110][111][112][113]. The data analysis suggested that ligand 14 forms exclusively monomeric species in high yields with Ni(II) and Pd(II).…”

“…Several studies were also directed to unravel how the increased flexibility of ligand 14 compared to 1 would affect its tendency to form trans-coordinating complexes concluding that it does not have a detrimental effect [109,110]. Many trans-complexes of ligand 14 have been synthesized as Ni14X 2 (X = Cl, I, NCS, CN), Pd14X 2 (X = Cl, Br, I, ONO, N 3 ), Pt14X 2 (X = Br, I, Cl), Pt14HCl, Pt14HBr, Ag14Cl or Rh14(CO)Cl and fully characterized by spectroscopic techniques [110][111][112][113].…”