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Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis.
Inorg Chem. 2009 May 04; 48(9):4118-33.IC

Abstract

The homodinuclear [ClM(mu-dppm)(2)MCl] complexes 1 (M = Pd) and 2 (M = Pt) react with RNC ligands (R = Ph, xylyl, p-tolyl, p-C(6)H(4)iPr) to provide the A-frame [ClPd(mu-dppm)(2)(mu-C=N-R)PdCl] (R = Ph (5a), xylyl (5b)), [ClPt(mu-dppm)(2)(mu-C=N-R)PtCl] (R = p-tolyl (4a); p-C(6)H(4)iPr (4b)), and the d(9)-d(9) M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (R = xylyl (3a); p-C(6)H(4)iPr (3b)) complexes. The heterodinuclear [XPd(mu-dppm)(2)PtX] complexes 6a (X = Cl) and 6b (X = I) react with RNC (R = o-anisyl) to form the A-frame [XPd(mu-dppm)(2)(mu-C=N-R)PtX] (X = Cl (9); I (10a)) and M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (10b) complexes. The dangling ligand-containing complex [ClPd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4)) (7) reacts with xylyl-NC stoichiometrically to produce the dicationic salt [(xylyl-NC)Pd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4))(2) (8). Parameters ruling the coordination site terminal versus bridging are discussed. The precursor 10a reacts with RNC (R = o-anisyl, tBu) to form the heterobimetallic bis(isonitrile) [IPd(mu-dppm)(2)(mu-C=N-o-anisyl)Pt(CN-R)]I complexes 11b and 12, respectively, demonstrating the site selectivity of the second CNR ligand coordination, Pd versus 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 d(9)-d(9) terminal and d(8)-d(8) A-frame homo- and heterodinuclear complexes in 2-MeTHF at 77 K were studied by UV-vis and luminescence spectroscopy. Assignments for the lowest energy absorption and emission bands are made on the basis of density functional theory and time-dependent density functional theory computations.

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Authors+Show Affiliations

Clément S
Institut UTINAM UMR CNRS 6213, Université de Franche-Comté, 16 route de Gray, 25030 Besançon, France.
Aly SM
No affiliation info available
Bellows D
No affiliation info available
Fortin D
No affiliation info available
Strohmann C
No affiliation info available
Guyard L
No affiliation info available
Abd-El-Aziz AS
No affiliation info available
Knorr M
No affiliation info available
Harvey PD
No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

19348458

Citation

Clément, Sébastien, et al. "Properties of the [M(dppm)2M']2+ Building Blocks (M, M' = Pd or Pt): Site Selectivity, Emission Features, and Frontier Orbital Analysis." Inorganic Chemistry, vol. 48, no. 9, 2009, pp. 4118-33.
Clément S, Aly SM, Bellows D, et al. Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis. Inorg Chem. 2009;48(9):4118-33.
Clément, S., Aly, S. M., Bellows, D., Fortin, D., Strohmann, C., Guyard, L., Abd-El-Aziz, A. S., Knorr, M., & Harvey, P. D. (2009). Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis. Inorganic Chemistry, 48(9), 4118-33. https://doi.org/10.1021/ic8023315
Clément S, et al. Properties of the [M(dppm)2M']2+ Building Blocks (M, M' = Pd or Pt): Site Selectivity, Emission Features, and Frontier Orbital Analysis. Inorg Chem. 2009 May 4;48(9):4118-33. PubMed PMID: 19348458.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Properties of the [M(dppm)2M']2+ building blocks (M, M' = Pd or Pt): site selectivity, emission features, and frontier orbital analysis. AU - Clément,Sébastien, AU - Aly,Shawkat M, AU - Bellows,Diana, AU - Fortin,Daniel, AU - Strohmann,Carsten, AU - Guyard,Laurent, AU - Abd-El-Aziz,Alaa S, AU - Knorr,Michael, AU - Harvey,Pierre D, PY - 2009/4/8/entrez PY - 2009/4/8/pubmed PY - 2009/4/8/medline SP - 4118 EP - 33 JF - Inorganic chemistry JO - Inorg Chem VL - 48 IS - 9 N2 - The homodinuclear [ClM(mu-dppm)(2)MCl] complexes 1 (M = Pd) and 2 (M = Pt) react with RNC ligands (R = Ph, xylyl, p-tolyl, p-C(6)H(4)iPr) to provide the A-frame [ClPd(mu-dppm)(2)(mu-C=N-R)PdCl] (R = Ph (5a), xylyl (5b)), [ClPt(mu-dppm)(2)(mu-C=N-R)PtCl] (R = p-tolyl (4a); p-C(6)H(4)iPr (4b)), and the d(9)-d(9) M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (R = xylyl (3a); p-C(6)H(4)iPr (3b)) complexes. The heterodinuclear [XPd(mu-dppm)(2)PtX] complexes 6a (X = Cl) and 6b (X = I) react with RNC (R = o-anisyl) to form the A-frame [XPd(mu-dppm)(2)(mu-C=N-R)PtX] (X = Cl (9); I (10a)) and M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (10b) complexes. The dangling ligand-containing complex [ClPd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4)) (7) reacts with xylyl-NC stoichiometrically to produce the dicationic salt [(xylyl-NC)Pd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4))(2) (8). Parameters ruling the coordination site terminal versus bridging are discussed. The precursor 10a reacts with RNC (R = o-anisyl, tBu) to form the heterobimetallic bis(isonitrile) [IPd(mu-dppm)(2)(mu-C=N-o-anisyl)Pt(CN-R)]I complexes 11b and 12, respectively, demonstrating the site selectivity of the second CNR ligand coordination, Pd versus 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 d(9)-d(9) terminal and d(8)-d(8) A-frame homo- and heterodinuclear complexes in 2-MeTHF at 77 K were studied by UV-vis and luminescence spectroscopy. Assignments for the lowest energy absorption and emission bands are made on the basis of density functional theory and time-dependent density functional theory computations. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/19348458/Properties_of_the_[M_dppm_2M']2+_building_blocks__M_M'_=_Pd_or_Pt_:_site_selectivity_emission_features_and_frontier_orbital_analysis_ L2 - https://doi.org/10.1021/ic8023315 DB - PRIME DP - Unbound Medicine ER -