Pyridine-2-selenolate and -2-tellurolate as ligands: a multinuclear (⁷⁷Se, ¹¹⁹Sn, ¹²⁵Te) magnetic resonance study of some tin(IV) complexes, and X-ray structural analyses of Sn(SPh)₂(2-Se-C₅H₄N-N,Se)₂ and Sn(SPh)_1.85(2-Se-C₅H₄N)_2.15

Abstract

Abstract:Reactions between Sn(EfPh), (E' = S or Se; n = 2 or 4) and the bis(pyridine) dichalcogenides 2,2'-(C,H,NE), (E = Se or Te), abbreviated py2E2, have been studied using multinuclear (77Se, lI9.Sn, I2,~e) magnetic resonance. In this way the occurrence of the pyridine-2-chalcogenate complexes Sn(EfPh),-,(Epy), (E' = S or Se; E = Se, x = 1 4 ; E = Te, x = 1 or 2) has been demonstrated. The pattern of 1 1 9~n NMR chemical shifts for Sn(EfPh),-,(Sepy), (E' = S or Se, x = 0-4) is consistent with bidentate bonding for the pySe-ligand when x = 1 and 2. The pyTe-ligand is probably bidentate also in all four complexes containing this ligand. As part of the NMR analysis, 7 7~e and (or) 12,~e NMR data were obtained for py,Te, and for the new mixed dichalcogenides PhE'ER (E' = S, Se, or Te; E # E' = Se or Te; R = 2-py or Ph), which were produced in the systems Ph2Ef2:R2E2. The complex Sn(SPh),(Sepy), (1) was isolated pure and its structure determined by the single crystal X-diffraction technique. The compound crystallizes in the monoclinic space group P2,ln, with unit cell dimensions a = 9.7929(9) A, b = 22.340(2) A, c = 11.368(1) A, P = 108.803 (7) (1)' and 65.8(1)". En route to 1, the yellow crystalline compound Sn(SPh),,,,(2-Se-C,H,N),,,, (2) was isolated. This was shown by l i 9~n NMR spectroscopy to contain both Sn(2-Se-C,H,N),(SPh), and Sn(2-Se-C,H,N),(SPh). The crystal and molecular structure of 2 was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P2,ln, a = 9.795(2) A, b = 22.355(4) A, c = 11.362(2) A, P = 108.87(3)", V = 2354.2(8) A3, dcalc = 1.837 g ~m -~, dabs = 1.87(5) g ~m -~, Z = 4, R1 = 0.0306, wR2 = 0.065 1 for 2756 data (F, 2 4u(F0)) and 258 parameters.Crystallographic evidence for the presence of co-crystallized Sn(2-Se-C,H,N),(SPh) occurs only in a minor lengthening of one of the two Sn-S bonds, Sn-S(1) (compared with expectation for I), and an excess of electron density at S(l) when the data are modelled as Sn(2-Se-C,H,N),(SPh),. These effects are attributed to a crystallographic disorder of SPh and 9 1 -{ 2 -~e -~5~4~} at the S(1)Ph site, involving isostructural S~(~~-{~-S~-C~H,N}),((~~-{~-S~-C,H,N})(SP~) and S~(~~-{~-S~-C,H,N})~(SP~),.Key words: pyridine-2-selenolate, pyridine-2-tellurolate, tin complexes.RCsumC : Utilisant la rCsonnance magnCtique de noyaux multiples ( 7 7~e , Il9sn, Iz5~e), on a CtudiC les rkactions entre le Sn(EfPh), (E' = S ou Se; n = 2 ou 4) et les dichalcogCnures de bis(pyridine) 2,T-(C,H,NE), (E = Se ou Te), reprksentks en abrkgk par py,E,. On a pu ainsi dCmontrer la formation des complexes 2-chalcogCnates de pyridine Sn(EfPh),-,(Epy), (E' = S ou Se; E = Se, x = 1 4 ; E = Te, x = 1 ou 2). L'allure des dkplacements chimiques de la RMN du " 9~n du composC Sn(EfPh),-,(Sepy), (E' = S ou Se, x = 0-4) est en accord avec une liaison bidentate pour le ligand pySe-lorsque x = 1 et 2. Le ligand pyTe-est probablement bidentate dans tous les quatre complexes oh on le retrouve Cgalement. Dans le cadre de cette analyse par RMN, on obten...

Dichloridobis(pyridine-2-selenolato-κ2N,Se)tin(IV)

“…The two Sn-Cl, two Sn-N and two Sn-Se bonds are in cis, cis and trans configurations, respectively. The lengths of the two covalent Sn-Se bonds [2.5917 (3) Å] are in good accordance with those in the previously studied analogous octahedral tin(IV) complexes (Labisbal et al, 1993;Chopra et al, 1996).…”

“…For metal complexes with 2,2 0 -dipyridyl dichalcogenides, see: Kadooka et al (1976a,b); Cheng et al (1996); Kienitz et al (1996); Bell et al (2000); Kita et al (2001); Kedarnath et al (2009). For syntheses and structures of related tin(IV) compounds, see: Masaki & Matsunami (1976); Masaki et al (1978); Labisbal et al (1993); Chopra et al (1996); Ismaylova et al (2012). Hydrogen-bond geometry (Å , ).…”

Diorganodiselenides and zinc(ii) organoselenolates containing (imino)aryl groups of type 2-(RNCH)C6H4

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The presence of an organic group containing donor atoms available for intramolecular coordination provides increased stability of the monomeric Main Group metal selenolates. [20][21][22][23][24][25][26][27][28][29] The Group 12 metal selenolates have raised considerable interest as single-source precursors for CVD processes. 30 Different strategies have been used in order to avoid polymerization, to stabilize monomeric species or, at least, to reduce the degree of oligomerization for Group 12 metal selenolates, i.e.…”