Ditin(IV) chalcogenide anions: Se-77, Sn-119, and Te-125 solution NMR study of the Sn(2)Ch(6)(4-) and Sn(2)Ch(7)(4-) (Ch=Se, Te) anions, X-ray crystal structures and Raman spectra of K+(N(CH3)(4)(+))(3)Sn2Se64-, (enH(+))(2)(2,2,2-crypt-K+)(2)Sn2Se64-, and (K+)(2)(2,2,2-crypt-K+)(2)Sn2Te64-, and X-ray crystal structures of K+(2,2,2-crypt-K+)(2)HOSnTe33- and K+(2,2,2-crypt-K+)(2)HOSnTe33-center dot en

被引:40
作者
Campbell, J [1 ]
Devereux, LA [1 ]
Gerken, M [1 ]
Mercier, HPA [1 ]
Pirani, AM [1 ]
Schrobilgen, GJ [1 ]
机构
[1] MCMASTER UNIV,DEPT CHEM,HAMILTON,ON L8S 4M1,CANADA
关键词
D O I
10.1021/ic950917c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The seleno- and tellurostannate(IV) anions Sn(2)Ch(6)(4-) and Sn(2)Ch(7)(4-) (Ch = Se, Te) have been obtained by extraction of the ternary alloys KSn0.67Se1.93 and KSn0.63Te1.70 in ethylenediamine (en) and/or liquid NH3 in the absence and in the presence of nonstoichiometric amounts of 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]-hexacosane) with respect to K+. The anions were characterized in solution for the first time by natural abundance Se-77, Sn-119, and Te-125 NMR spectroscopy. The magnitudes of the relativistically corrected reduced coupling constants K-1(Sn-Ch(t))(RC), K-1(Sn-Ch(mb))(RC), and K-1(Sn-Ch(db))(RC) were shown to be consistent with a significant degree of s-character in the bonding. The Sn-Ch(mb) and Sn-Ch(t) bond distances observed for the dimeric SnCh(3)(2-) anions, namely Sn(2)Ch(6)(4-), in K+(N(CH3)(4)(+))(3)Sn2Se64- (1), (enH(+))(2)(2,2,2-crypt-K+)(2)Sn2Se64- (2), and (K+)(2)(2,2,2- crypt-K+)(2)Sn2Te64- (3) were shown to correlate with the K-1(Sn-Ch)(RC) values, indicating that the solid-state molecular structures of the anions are retained in solution. The Raman spectra of compounds 1-3 are also reported along with their respective factor-group analyses. The novel HOSnTe33- anion, the hydroxide derivative of the SnTe32- anion, has been structurally characterized by X-ray crystallography in K+(2,2,2-crypt-K+)(2)HOSnTe33- (4) and in K+(2,2,2-crypt-K+)(2)HOSnTe33-. en (5) and represents the first example of a simple mixed hydroxychalcogenide anion of tin.
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页码:2945 / 2962
页数:18
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