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Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations
Authors: Wagner Michael | Deáky Vajk | Dietz Christina | Martincová Jana | Mahieu Bernard | Jambor Roman | Herres-Pawlis Sonja | Jurkschat Klaus
Year: 2013
Type of publication: článek v odborném periodiku
Name of source: Chemistry - A European Journal
Publisher name: Wiley-VCH
Place: Weinheim
Page from-to: 6695-6708
Titles:
Language Name Abstract Keywords
cze Studie Intramolekulárně koordinovaných Stannylenových komplexů Pd a Pt: Syntéza, Struktura a Reaktivita Syntéza stannylenových komplexů Pd a Pt 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) a trans-[(4-tBu-2,6-{P(O)(OiPr)2}2 C6H2SnCl)PdI2]2 (8) je publikována. Dále pak byl připraven komplex trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2 Pt(SnCl3)2] (10) a [(4-tBu-2,6-{P(O) (OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11). Sloučeniny byly chyrakterizované pomocí 1H, 13C, 31P, 119Sn a 195Pt NMR spektroskopie. DFT kalkulace; paladium; platina; komplexy
eng Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations 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}2 C6H2SnCl)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)2 Pt(SnCl3)2] (10) and [(4-tBu-2,6-{P(O) (OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11). The compounds were characterised by elemental analyses, 1H, 13C, 31P, 119Sn and 195PtNMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Mossbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Mossbauer 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-(Me2NCH2)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. density functional calculations; palladium; platinum; structure elucidation; tin; transition metals

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