Properties of the [M(dppm)2M']2+ building blocks ...

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Title Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis.
Author(s) Sebastien Clement, Shawkat M. Aly, Diana Bellows, Daniel Fortin, Carsten Strohmann, Laurent Guyard, Alaa S. Abd-El-Aziz, Michael Knorr, Pierre D. Harvey
Journal Section Title: Inorganic Chemicals and Reactions, Inorganic Chemistry (Washington, DC, United States)
Date 2009
Volume 48
Issue 9
Start page 4118
End page 4133
Abstract The homodinuclear [ClM(μ-dppm)2MCl] complexes 1 (M = Pd) and 2 (M = Pt) react with RNC ligands (R = Ph, xylyl, p-tolyl, p-C6H4iPr) to provide the A-frame [ClPd(μ-dppm)2(μ-C:N-R)PdCl] (R = Ph (5a), xylyl (5b)), [ClPt(μ-dppm)2(μ-C:N-R)PtCl] (R = p-tolyl (4a); p-C6H4iPr (4b)), and the d9-d9 M2-bonded [ClPt(μ-dppm)2Pt(CN-R)]Cl (R = xylyl (3a); p-C6H4iPr (3b)) complexes. The heterodinuclear [XPd(μ-dppm)2PtX] complexes 6a (X = Cl) and 6b (X = I) react with RNC (R = o-anisyl) to form the A-frame [XPd(μ-dppm)2(μ-C:N-R)PtX] (X = Cl (9); I (10a)) and M2-bonded [ClPt(μ-dppm)2Pt(CN-R)]Cl (10b) complexes. The dangling ligand-contg. complex [ClPd(μ-dppm)2Pt(η1-dppm:O)](BF4) (7) reacts with xylyl-NC stoichiometrically to produce the dicationic salt [(xylyl-NC)Pd(μ-dppm)2Pt(η1-dppm:O)](BF4)2 (8). Parameters ruling the coordination site terminal vs. bridging are discussed. The precursor 10a reacts with RNC (R = o-anisyl, tBu) to form the heterobimetallic bis(isonitrile) [IPd(μ-dppm)2(μ-C:N-o-anisyl)Pt(CN-R)]I complexes 11b and 12, resp., demonstrating the site selectivity of the second CNR ligand coordination, Pd vs. Pt. The x-ray structures of 11b and 12 were obtained. Complex 12 is the first example of an A-frame system of the Ni-triad bearing two different isocyanide ligands. Several d9-d9 terminal and d8-d8 A-frame homo- and heterodinuclear complexes in 2-MeTHF at 77 K were studied by UV-visible and luminescence spectroscopy. Assignments for the lowest energy absorption and emission bands are made from d. functional theory and time-dependent d. functional theory computations. [on SciFinder(R)]
DOI 10.1021/ic8023315

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