Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations1. Issue 21 (27th March 2013)

• Record Type: Journal Article
• Authors: Wagner, Michael; Deáky, Vajk; Dietz, Christina; Martincová, Jana; Mahieu, Bernard; Jambor, Roman; Herres‐Pawlis, Sonja; Jurkschat, Klaus
• Is Part Of: Chemistry. Volume 19:Issue 21(2013)
• Page Start: 6695
• Page End: 6708
• Publication Date: 2013-03-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201203511
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The syntheses of the transition metal complexes <italic>cis</italic>‐[(4‐<italic>t</italic>Bu‐2, 6‐{P(O)(O<italic>i</italic>Pr)<sub>2</sub>}<sub>2</sub>C<sub>6</sub>H<sub>2</sub>SnCl)<sub>2</sub>MX<sub>2</sub>] (<bold>1</bold>, M=Pd, X=Cl; <bold>2</bold>, M=Pd, X=Br; <bold>3</bold>, M=Pd, X=I; <bold>4</bold>, M=Pt, X=Cl), <italic>cis</italic>‐[{2, 6‐(Me<sub>2</sub>NCH<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>SnCl}<sub>2</sub>MX<sub>2</sub>] (<bold>5</bold>, M=Pd, X=I; <bold>6</bold>, M=Pt, X=Cl), <italic>trans</italic>‐[{2, 6‐(Me<sub>2</sub>NCH<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>SnI}<sub>2</sub>PtI<sub>2</sub>] (<bold>7</bold>) and <italic>trans</italic>‐[(4‐<italic>t</italic>Bu‐2, 6‐{P(O)(O<italic>i</italic>Pr)<sub>2</sub>}<sub>2</sub> C<sub>6</sub>H<sub>2</sub>SnCl)PdI<sub>2</sub>]<sub>2</sub> (<bold>8</bold>) are reported. Also reported is the serendipitous formation of the unprecedented complexes <italic>trans</italic>‐[(4‐<italic>t</italic>Bu‐2, 6‐{P(O)(O<italic>i</italic>Pr)<sub>2</sub>}<sub>2</sub>C<sub>6</sub>H<sub>2</sub>SnCl)<sub>2</sub> Pt(SnCl<sub>3</sub>)<sub>2</sub>] (<bold>10</bold>) and [(4‐<italic>t</italic>Bu‐2, 6‐{P(O) (O<italic>i</italic>Pr)<sub>2</sub>}<sub>2</sub>C<sub>6</sub>H<sub>2</sub>SnCl)<sub>3</sub>Pt(SnCl<sub>3</sub>)<sub>2</sub>] (<bold>11</bold>). The compounds were characterised by elemental analyses, <sup>1</sup>H, <sup>13</sup>C, <sup>31</sup>P, <sup>119</sup>Sn and <sup>195</sup>Pt NMR spectroscopy, single‐crystal X‐ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds <bold>1</bold>, <bold>3</bold> and <bold>4</bold>, 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 <bold>1</bold> and <bold>3</bold> as well as between <bold>1</bold> and <italic>cis</italic>‐[{2, 6‐(Me<sub>2</sub>NCH<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>SnCl}<sub>2</sub>PdCl<sub>2</sub>]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the <italic>cis</italic> and <italic>trans</italic> isomers. The latter is influenced by the donor strength of the pincer‐type ligands.</p> </abstract>