Ultraviolet Absorption Spectra of Perethylpolygermanes and -Polystannanes

Drenth, W.; Noltes, J. G.; Bulten, E.J.; Creemers, H.M.J.C.

doi:10.1016/s0022-328x(00)88054-7

Cited by 35 publications

(29 citation statements)

References 6 publications

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“…Compared to the higher Group 14 elements silicon and germanium, tin forms the weakest covalent metal-metal bonds [8][9][10] (BDE for single r bond: Sn-Sn 146 kJ/mol, Ge-Ge 188 kJ/mol, Si-Si 222 kJ/mol) [11]; oligo-and polystannanes do not easily remain as catenates and show increased sensitivity to light and moisture. Tin catenates are interesting for the fact that, structurally, they resemble saturated hydrocarbons, yet they exhibit conjugation that is more typical of p-bonded alkenes.…”

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confidence: 99%

Linear Oligostannanes: A Synthetic and TD-DFT Study

Harrypersad

Liao

Khan

et al. 2015

J Inorg Organomet Polym

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A series of model linear tristannanes [(( 1 R) 3-Sn) 2 ( 2 R) 2 Sn (1: 1 R = 2 R = n-Bu, 2: 1 R = Ph, 2 R = n-Bu, 3: 1 R = Me, 2 R = n-Bu, 4: 1 R = n-Bu, 2 R = Ph, 5: 1 R = Me, 2 R = Ph, 6: 1 R = n-Bu, 2 R = Me, 7: 1 R = Ph, 2 R = Me)] were prepared by condensation reactions of one equivalent of a dialkyl or diaryl tin diamide or dihydride and two equivalents of a trialkyl or triaryl tin hydride or amide respectively, and characterized by NMR ( 1 H, 13 C, 119 Sn) and UV-Vis spectroscopy, and elemental analysis. An LSDA/SDD level of DFT and TD-DFT for trimers 1-7 predicts significant structural differences as a function and nature of the substituents bound to tin and calculated electronic transitions for these compounds in fair relative agreement with experimental results. Calculated electronic spectra obtained from equivalent DFT studies of the sequentially lengthened oligomers Ph 3 Sn[t-Bu 2 Sn] n SnPh 3 (8-11 where n = 1-4) previously prepared by Dräger are in good agreement with the reported experimental UVVisible spectroscopic and X-ray diffraction data which show a red shift of the r-r* absorption transition (k max ) and bond lengthening and bond angle widening of the central tin atoms as the oligostannane is extended. TD-DFT studies of the alkoxy terminated di(n-butyl) oligostannanes 12a-m (CH 3 CH 2 OCH 2 CH 2 [Sn(n-Bu) 2 ] n CH 2 CH 2 OCH 2 CH 3 ); n = 3-15) indicate lower limiting energy gaps as the polymer chain size is increased. The calculated data deviates significantly from results found experimentally by Sita and suggests that even smaller energy gaps are possible if the polymer (13) resides in an all trans configuration. TD-DFT studies at the LSDA/SDD level were also carried out on a model polystannane 16 (H[SnH 2 ] n H, n = 1-40) to investigate the impact of Sn catenation on the intrinsic band gap of the material and compared to both the Si and Ge analogues 14 and 15 (H[MH 2 ] n H, M = Si, Ge: n = 1-40). The modelling of the polymetallanes reveals the expected limiting energy gap of the r-r* transition in a trans-planar configuration with Sn (2.681 eV) \ Ge (3.096 eV) \ Si (3.719 eV) in good agreement with previous studies by Takeda. Finally, comparison of the TD-DFT calculated data for model alternating oligostannanes (17)(18)(19) with the UV-Vis spectroscopic data for alternating polystannanes (20-22) recently prepared by polycondensation is made.

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confidence: 99%

Linear Oligostannanes: A Synthetic and TD-DFT Study

Harrypersad

Liao

Khan

et al. 2015

J Inorg Organomet Polym

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“…The syntheses of high molecular weight poly(dialkyl)stannanes (26) 82,90 and poly(diaryl)stannanes (27) 97,100 using different Cp 2 ZrR 2 derivatives as catalysts were reported. The most active catalyst reported so far for the synthesis of high molecular weight poly(dibutyl)stannanes is Me 2 C(η 5 -C 5 H 4 ) 2 Zr[Si(SiMe 3 ) 3 ]Me (24). It was claimed to produce H(n-Bu 2 Sn) n H (26) 82 with a molecular weight up to M w = 6.69 × 10 4 and a molecular weight distribution of M w /M n = 3.30.…”

Section: Polystannanesmentioning

confidence: 99%

“…To date, the highest nuclearity observed in oligomeric organotin compounds is twelve. Several derivatives of the isostructural fragment [(RSn) 12 (µ 3 -O) 14 (µ-OH) 6 24 ] 4+ , which additionally encapsulates a Na + ion in the organotin oxide core 225 231 . In polymeric chains of triorganotin fluorides, the tin atom is five-coordinate and has a trigonal bipyramidal configuration with the fluorine atoms in axial positions.…”

Section: A Organotin Polymersmentioning

confidence: 99%

“…One-dimensional zigzag chain structures with pentacoordinated lead atoms are also adopted by trimethyllead carboxylates (174). The intramolecular and the intermolecular Pb−O distances in trimethyllead acetate, Me 3 Pb(OOCCH 3 ) (174a) 456 , amount to 2.327 (24) 2 459 , and phenyllead triacetate, PhPb(OAc) 3 459 , are monomeric in the solid state with hexacoordinated and heptacoordinated lead atoms, respectively, and unsymmetrically chelating acetate groups.…”

Section: Intermolecular Organolead-oxygen Coordinationmentioning

confidence: 99%

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Organometallic Polymers of Germanium, Tin and Lead

Jurkschat

Mehring

2009

Patai's Chemistry of Functional Groups

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“…In this field, some valuable results have been obtained from the oxidative addition of germanium-containing diselenides to a macrocyclic square planar complex of rhodium(1) [12]. It is assumed from spectroscopic data and theoretical calculation that conduction might result from introduction of electrons from the electron-rich rhodium atom into the suitable band gap of the germanium-containing chain [27].…”

Section: Introductionmentioning

confidence: 99%