Subvalent Group 4B metal alkyls and amides. Part III Mössbauer spectroscopy studies of bis[bis(trimethylsilyl)methyl]tin(<scp>II</scp>) and its derivatives

Cotton, John D.; Davidson, Peter; Läppert, Michael F.; Donaldson, J. D.; Silvet, Jack

doi:10.1039/dt9760002286

Cited by 62 publications

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“…[53] In complexes 1-6, the organostannylenes RSnCl (R = 4-tBu-2,6-[P(O)A C H T U N G T R E N N U N G (OiPr) 2 ] 2 C 6 H 2 , 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ) are mutually cis coordinated with the Sn-M-Sn angles ranging between 96.37(2) (1) and 100.33(2)8 (6). These IS values are very unusual and lie out of the range generally observed for organoA C H T U N G T R E N N U N G tin(II) (2.10-3.00 mm s À1 ) [55] and organotin(IV) compounds (1.1-1.6 mm s À1 ), [56] which suggests that the tin atoms in 3 and 4 have an oxidation state of III. [54] DFT calculations (see below) suggest that these are bonding interactions.…”

Section: Resultsmentioning

confidence: 77%

“…The Mçssbauer spectra of compounds 3 and 4 show isomer shifts (ISs) of 1.81 (quadrupole splitting, QS = 3.51 mm s À1 ) and 1.70 mm s À1 (QS = 3.48 mm s À1 ), respectively. These IS values are very unusual and lie out of the range generally observed for organoA C H T U N G T R E N N U N G tin(II) (2.10-3.00 mm s À1 ) [55] and organotin(IV) compounds (1.1-1.6 mm s À1 ), [56] which suggests that the tin atoms in 3 and 4 have an oxidation state of III. This view is correct when considering mainly covalent bonds to the three more electronegative carbon, chlorine or iodine, and palladium atoms.…”

Section: Resultsmentioning

confidence: 80%

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Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations

Wagner

Deáky

Dietz

et al. 2013

Chemistry A European J

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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.

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Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 80%

Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations

Wagner

Deáky

Dietz

et al. 2013

Chemistry A European J

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“…A stirred solution o f 2 (594 mg, 1.12 mmol) in toluene (7 mL) at 0°C was treated with an equimolar amount of tert-butyl cyanide or pyridiue. After a few seconds (4) or within several hours (3). the deep red solution changed color.…”

Section: Dedicated To Professor Edwin Hengge On the Occasion Of His 6mentioning

confidence: 99%

Bis(pentamethylcyclopentadienyl)silylene as Ligand in Gold(I) Chloride Complexes

Jutzi

Möhrke

1990

Angew. Chem. Int. Ed. Engl.

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The first real silylene complex was obtained by reaction of decamethylsilicocene 1 with carbonylgold(I) chloride. To reduce the electron deficit at the silicon in 2, one of the two cyctopentadienyl ligands remains π‐bonded. The deep‐red silylene complex 2 resembles the Fischer carbene complexes. Addition of pyridine or tert‐butyl isocyanide leads to the donor‐stabilized silylene complexes of the type (Me5C5)2Si(donor)–AuCl, in which both cyclopentadienyl ligands are σ‐bound.

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“…There are two possible ways of describing the hybridization of the Te atoms; either sp 2 or sp 3 in a similar manner to that for Sn H (Cotton, Donaldson, Lappert & Silver, 1976). In the former, the Te atom is considered to have a trigonal planar arrangement, with two bonds to C and a lone pair of electrons in the equatorial plane.…”

Section: Discussionmentioning

confidence: 99%

Studies on tellurium–carbon bonded compounds. III. The crystal structure of acetylacetone tellurium(II)

Dewan¹,

Silver²

1977

Acta Crystallogr Sect B

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The structure of the title compound has been determined by the heavy-atom method from 685 reflexions, measured with a diffractometer, and refined by full-matrix least-squares methods to R 3-4%. Crystals are orthorhombic, space group Iba2, a = 22.35 (3), b = 10.78 (2), c = 5.26 (1) A, Z = 8. In the molecules of the complex a Ten atom is bonded to one bivalent acetylacetone ligand via the a-C atoms ITe-C 2.17 (1), 2.15 (1) A; C-Te--C 90.8 (4) °] forming a heterocyclic ring of chair conformation. The molecules are arranged into one-dimensional polymers parallel to [0011 by associations between the Te atoms; the implications of these associations with regard to the colour of this and related tellurium compounds are discussed in the light of present theories. H atoms could not be located.

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Subvalent Group 4B metal alkyls and amides. Part III Mössbauer spectroscopy studies of bis[bis(trimethylsilyl)methyl]tin(II) and its derivatives

Abstract: Subvalent Group 4 8 Metal Alkyls and Amides. Part 111.l Mossbauer Spectroscopy Studies of Bis[bis(trimethylsilyl)methyl]tin(ii) and its D e r i vat i ves t

Cited by 62 publications

References 0 publications

Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations

Insights into the Intramolecular Donor Stabilisation of Organostannylene Palladium and Platinum Complexes: Syntheses, Structures and DFT Calculations

Bis(pentamethylcyclopentadienyl)silylene as Ligand in Gold(I) Chloride Complexes

Studies on tellurium–carbon bonded compounds. III. The crystal structure of acetylacetone tellurium(II)

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