title: Insights into the intramolecular donor stabilisation of organostannylene palladium and platinum complexes: syntheses, structures and DFT calculations.
abstract: The syntheses of the transition metal complexes cis-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2MX2] (1, M = Pd, X = Cl; 2, M = Pd, X = Br; 3, M = Pd, X = I; 4, M = Pt, X = Cl), cis-[{2,6-(Me2NCH2)2C6H3SnCl}2MX2] (5, M = Pd, X = I; 6, M = Pt, X = Cl), trans-[{2,6-(Me2NCH2)2C6H3SnI}2PtI2] (7) and trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)PdI2]2 (8) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2Pt(SnCl3)2] (10) and [(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11). The compounds were characterised by elemental analyses, (1)H, (13)C, (31)P, (119)Sn and (195)Pt NMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Mössbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Mössbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me2 NCH2)2C6H3SnCl}2PdCl2]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands.
authors.affiliation: Lehrstuhl für Anorganische Chemie II, Technische Universität Dortmund, 44221 Dortmund, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Wagner
authors.forename: Vajk
authors.initials: V
authors.lastname: Deáky
authors.forename: Christina
authors.initials: C
authors.lastname: Dietz
authors.forename: Jana
authors.initials: J
authors.lastname: Martincová
authors.forename: Bernard
authors.initials: B
authors.lastname: Mahieu
authors.forename: Roman
authors.initials: R
authors.lastname: Jambor
authors.forename: Sonja
authors.initials: S
authors.lastname: Herres-Pawlis
authors.forename: Klaus
authors.initials: K
authors.lastname: Jurkschat