Metal−Metal Interactions in Heterobimetallic d⁸−d¹⁰Complexes. Structures and Spectroscopic Investigation of [M‘M‘ ‘(μ-dcpm)₂(CN)₂]⁺(M‘ = Pt, Pd; M‘ ‘ = Cu, Ag, Au) and Related Complexes by UV−vis Absorption and Resonance Raman Spectroscopy and ab Initio Calculations

Abstract

X-ray structural and spectroscopic properties of a series of heterodinuclear d(8)-d(10) metal complexes [M'M' '(mu-dcpm)(2)(CN)(2)](+) containing d(8) Pt(II), Pd(II), or Ni(II) and d(10) Au(I), Ag(I), or Cu(I) ions with a dcpm bridging ligand have been studied (dcpm = bis(dicyclohexylphosphino)methane; M' = Pt, M' ' = Au 4, Ag 5, Cu, 6; M' ' = Au, M' = Pd 7, Ni 8). X-ray crystal analyses showed that the metal...metal distances in these heteronuclear metal complexes are shorter than the sum of van der Waals radii of the M' and M' ' atoms. The UV-vis absorption spectra of 4-6 display red-shifted intense absorption bands from the absorption spectra of the mononuclear trans-[Pt(phosphine)(2)(CN)(2)] and [M' '(phosphine)(2)](+) counterparts, attributable to metal-metal interactions. The resonance Raman spectra confirmed assignments of (1)[nd(sigma)-->(n + 1)p(sigma)] electronic transitions to the absorption bands at 317 and 331 nm in 4 and 6, respectively. The results of theoretical calculations at the MP2 level reveal an attractive interaction energy curve for the skewed [trans-Pt(PH(3))(2)(CN)(2)-Au(PH(3))(2)(+)] dimer. The interaction energy of Pt(II)-Au(I) was calculated to be ca. 0.45 ev.

Binuclear Pd-methyl complexes of N,N′-{1, n}-alkanediyl-bis(pyridinyl-2-methanimine) ligands (n = 5, 8, 9, 10 and 12): Evaluation as catalysts precursors for phenylacetylene polymerization

“…Additional oxidation states might also be accessible to binuclear complexes as a result of possible stabilization via metalemetal interactions [4]. Interaction between nearby metal centers could potentially cause increased reaction rates or yield transformation rates not possible with mononuclear species [5].…”

Electrochemical oxidation of ethanol using Nafion electrodes modified with heterobimetallic catalysts

“…Using a heterometallic catalytic system allows the reactivities of one or more metals to be combined which in turn results in lower oxidation potentials and less catalyst poisoning [11][12][13][14][15][16].…”

Quantum chemistry studies on the Ru–M interactions and the 31P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M=Zn, Cd, Hg)

“…Over the past two decades, heterometallic complexes containing metal-metal bond have been extensively studied due to their unique structures and properties including catalysis [1][2][3][4][5][6] and spectroscopy [2,5,[7][8][9]. Much interest is focused on the study of polydentate ligands with maingroup donors that are able to form various polynuclear complexes, such as 2-(diphenylphosphino)pyridine (Ph 2 -Ppy) [2,3,5], 2,6-bis(diphenylphosphino)pyridine [2,5], bis(dimethylphosphino)methane(dmpm) [10], bis(diphenylphosphino)methane(dppm) [2,4].…”