Fragmentation of an imido tin(II) cubane; syntheses and structures of heterobimetallic complexes containing tin(II) imido and phosphinidine anions

Allan, R. E.; Beswick, Michael A.; Cromhout, Natalie L.; Paver, Michael A.; Raithby, Paul R.; Steiner, Alexander; Trevithick, Mark; Wright, Dominic S.

doi:10.1039/cc9960001501

Cited by 44 publications

(37 citation statements)

References 15 publications

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“…[8] Application of this methodology to imidotin cages involves the use of the amido/imido seco-cube [Sn 3 (m 3 -NtBu)(m 2 -NtBu)(m 2 -NHtBu) 2 ] (1) reported by Veith et al [9] We disclose here that the anionic cluster in [Li(thf) 4 ] [(thf)LiSn 3 (m 3 -NtBu) 4 ] (2 a), which is readily generated by dilithiation of 1 with nBuLi, exhibits a dramatic increase in the reactivity of the tin(ii) centers towards chalcogens compared to that of the neutral cluster [(Snm 3 -NtBu) 4 4 ] with three equivalents of C 10 H 7 NHLi. [10] The 1 H NMR spectrum of complex 2 a exhibits two resonances in a 3:1 ratio for the tBu protons, and a single resonance is observed in the 119 Sn NMR spectrum; both of these observations are consistent with local C 3 symmetry for the anion in 2 a. The 7 Li NMR spectrum of 2 a shows two well-separated resonances, indicating that the [Sn 3 Li(m 3 -NtBu) 4 ] cluster remains intact, even in THF solution.…”

Section: N]mentioning

confidence: 97%

Complete Chalcogenation of Tin(II) Centers in an Imidotin Cluster

Chivers

Eisler

2004

Angew Chem Int Ed

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The use of inorganic rings or clusters as precursors to industrially important materials such as inorganic polymers, [1] nanomaterials, [2] or semiconductors [3] represents an active area of contemporary inorganic chemistry. In the latter category the design of suitable precursors for the low bandgap semiconductors SnE (E = Se, Te), which have applications in thermoelectric devices and for optoelectronic materials, is of current interest. [4,5] Suitably chosen complexes containing terminal Sn = E bonds would appear to be candidates for this purpose.[6] In particular, imidotin chalcogenides of the type [(ESnm 3 -NR) 4 ] (E = Se, Te) may act as singlesource precursors of these binary semiconductors by the energetically favorable elimination of the diazene RN = NR. However, investigations of the reactions of the neutral cluster 4 ] with chalcogens have revealed that oxidation is limited to one tin(ii) center for E = Te (A) or two tin(ii) centers in the case of E = Se (B). [7] To address this synthetic challenge, we have adopted a strategy that was successful for the generation of the previously inaccessible PÀTe ligands[8]That approach involved the formation of anionic imidophosphorus(iii) reagents by metalation with NaH or nBuLi, prior to reaction with tellurium.[8]Application of this methodology to imidotin cages involves the use of the amido/imido seco-cube [Sn 3 (m 3 -NtBu)(m 2 -NtBu)(m 2 -NHtBu) 2 ] (1) reported by Veith et al. [9] We disclose here that the anionic cluster in [Li(thf) 4 ] [(thf)LiSn 3 (m 3 -NtBu) 4 ] (2 a), which is readily generated by dilithiation of 1 with nBuLi, exhibits a dramatic increase in the reactivity of the tin(ii) centers towards chalcogens compared to that of the neutral cluster 4 ] with three equivalents of C 10 H 7 NHLi.[10] The 1 H NMR spectrum of complex 2 a exhibits two resonances in a 3:1 ratio for the tBu protons, and a single resonance is observed in the 119 Sn NMR spectrum; both of these observations are consistent with local C 3 symmetry for the anion in 2 a. The 7 Li NMR spectrum of 2 a shows two well-separated resonances, indicating that the [Sn 3 Li(m 3 -NtBu) 4 ] cluster remains intact, even in THF solution.The reaction of 2 a with slightly more than three equivalents of selenium in THF readily produces the tristannaselone 3 a in essentially quantitative yields within several minutes at room temperature. Complex 3 b was obtained in a similar manner from 2 b and selenium. The tristannatellone 4 can also be synthesized from 2 a and a slight excess of tellurium at room temperature in about 1 h. However, the reaction proceeds more rapidly with gentle heating (20 min, 40 8C) to give 4 in 73 % yield. The mild reaction conditions necessary to produce the fully chalcogenated complexes 3 a, 3 b, and 4 are in striking contrast to those used to prepare the partially chalcogenated complexes A and B, which require boiling toluene and long reaction times (24-48 h).[7] Clearly, the negative charge in the anion of 2 a results in a dramatic enhancement of the susceptibility of ...

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Section: N]mentioning

confidence: 97%

Complete Chalcogenation of Tin(II) Centers in an Imidotin Cluster

Chivers

Eisler

2004

Angew Chem Int Ed

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“…It can be noted that the related reactions with metallated primary amines (RNHLi) do not produce related macrocyclic frameworks. [29] More recently, however, we have found that group-14 frameworks of this type can be obtained in a more straightforward manner by the direct reactions of Sn(NMe 2 ) 2 with RPHLi (Rϭ tBu, Cy) (Scheme 14). [31] This strategy is restricted to aliphatic phosphides and to Li as the metal, as extensive coupling of the RP groups occurs in reactions involving aromatic phosphides or with aliphatic phosphides of the heavier alkali metals.…”

Section: Valence-isoelectronic Macrocycles Containing Other P-block Ementioning

confidence: 99%

“…In practice the formation of isoelectronic anions of this type is not simple and different synthetic strategies have to be employed to those used in the related PϪN systems. One earlier synthetic approach which we employed is the ''templating'' reaction of cubanes such as [Sn(NtBu)] 4 (22) [29] Eur. J. Inorg.…”

Section: Valence-isoelectronic Macrocycles Containing Other P-block Ementioning

confidence: 99%

Toroidal Main Group Macrocycles: New Opportunities for Cation and Anion Coordination

2003

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Inorganic macrocycles, possessing molecular frameworks composed entirely of elements other than carbon, are rare. Even rarer are species analogous to classical organic macrocycles (like crown ethers) that possess the potential ability to coordinate metal ions within their cavities. Recent studies reveal an emerging structural class of valence‐isoelectronic main‐group ligands of general formula [{E(µ‐E′R)}2Y]nx−, which possess fascinating coordination characteristics. Such species can coordinate metal ions within their cavities (using the donor centres Y and E′), their peripheral donor centres (E′) (in an exo fashion) and are also capable of coordinating anions (where Y = N−H). This short review highlights the recent synthetic and structural studies of these unusual ligand systems and pinpoints potential future areas of development. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…During the last years we were interested in the syntheses and coordination chemistry of polyimido sulfur anions like S(NR) 3 2− ,1 S(NR) 4 2− ,2 RS(NR) 2 − 3 or RS(NR) 3 − ,4 the aza analogues of the well‐established oxo anions SO 3 2− , SO 4 2− , RSO 2 − , and RSO 3 − . The extensive interest in polyimido anions of the p‐block elements is evident from the syntheses of most E(NR) x n − anions during the last five to six years (E=S,1–4 Se,5 Te,6 P,7 As,8 Sb,9 C,10 Si,11, Sn12; x, n =1–4) and is still fuelled by various applications. Here we present the syntheses and structures of [{(thf)Li 2 [H 2 CS(N t Bu) 2 ]} 2 ] ( 1 ) and [{(thf)Li 2 [(Et)(Me)CS(N t Bu) 2 ]} 2 ] ( 2 ), the first carb/diaza analogues of SO 3 2− , in which two oxygen atoms are isoelectronically replaced by a N t Bu group each and the third oxygen atom is substituted by a CR 2 group.…”

Section: Introductionmentioning

confidence: 99%

A New Class of Dianionic Sulfur-Ylides: Alkylenediazasulfites

Walfort

Bertermann

2001

Chem. Eur. J.

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The compounds [[(thf)Li2-[H2CS(NtBu)2]]2] (1) and [((thf)Li2[(Et)-(Me)CS(NtBu)2])2] (2) can be synthesized in a two-step reaction. Firstly addition of an alkyllithium to sulfur diimide gives the diazaalkylsulfinate [RS(NtBu)2] (R =Me, sBu). In a second step the alpha-carbon atom in R is metalated with one equivalent of methyllithium to give the S-ylides. This new class of compounds can be rationalized as sulfite analogues, in which two oxygen atoms are each isoelectronically replaced by a NtBu group and the remaining oxygen atom is replaced by a CR2 group. Similar to Corey's S-ylides (R2(O)S+-CR2) and Wittig's phosphonium ylides (R3P+ - -CR2), these molecules contain a positively charged sulfur atom next to a carbanionic center. Therefore nucleophilic addition reactions of the carbon atom are feasible. The reaction of a sulfur diimide with the anionic carbon center in [H2CS-(NtBu)2]2- gives the intermediate alkylbis(diazasulfinate) [(tBuN)2SCH2S(NtBu)2]2-. The acidity of the hydrogen atoms at the bridging CH2 group is high enough to give, upon deprotonation, the [(tBuN)2SCHS(NtBu)2]3- trianion in [[(thf)Li3[(tBuN)2SCHS(NtBu)2]]2] (3). In [(Et)(Me)CS(NtBu)2]2 the nucleophilic carbon atom is sterically hindered and transimidation instead of deprotonation is observed. In a complex redox process [(thf)6Li6S((NtBu)3S]2] is recovered. The two new classes of compounds broaden the rich coordination chemistry of the triazasulfites by the introduction of a hard carbon center.

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Fragmentation of an imido tin(II) cubane; syntheses and structures of heterobimetallic complexes containing tin(II) imido and phosphinidine anions

Cited by 44 publications

References 15 publications

Complete Chalcogenation of Tin(II) Centers in an Imidotin Cluster

Complete Chalcogenation of Tin(II) Centers in an Imidotin Cluster

Toroidal Main Group Macrocycles: New Opportunities for Cation and Anion Coordination

A New Class of Dianionic Sulfur-Ylides: Alkylenediazasulfites

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