Self‐Assembly of Thirty‐Six Atom Clusters (Li₁₂S₆O₆N₁₂) Containing Diazasulfite Anions

Abstract

Recently there has been considerable interest in alkali metal derivatives of polyimido anions of p-block elements, for example [Sb(NR) [^-^^ The replacement of one (or more) of the bulky NR groups in the anions of these clusters by the isoelectronic 0x0 ligand may have significant structural consequences, but the diazasulfite anions [0S(NR)(NR)l2 (2) are unknown. We describe here the syntheses of dilithium derivatives of the bis(tert-buty1imido)sulfite dianion, [OS(N~BU),]* -(2a), and the (tert-butylimido)(trimethylsilylimido)sulfite dianion, [OS(NtBu)(NSiMe,)]* -(2b), which adopt unique cluster structures derived from the aggregation of hexagonal prisms and eighteen atom cages, respectively.: R N & + NRThe reactions of the chalcogen diimides, tBuN=E=NtBu, with two equivalents of LiNHtBu produce the dianions [E(NtBu>,l2-(E = S, Se, Te) in excellent y i e l d~. [~-~] By analogy, the treatment of tert-butylsulfinylimine, tBuNSO, or trimethylsilylsulfinylimine, Me,SiNSO, with two equivalents of lithium tert-butylamide leads to hexameric dilithium bis( tertbuty1imido)sulfite 3 and hexameric dilithium (tert-buty1imido)-(trimethylsily1imido)sulfite 4, respectively [Eq. (a), cf. reac-tions of RNSO with other bases, e.g. Li[N(SiMe,)R], which lead to mixed sulfurdiimides, RNSNR]A crystal structure determination of 3 revealed a remarkable arrangement of thirty-six atoms of main group elements in a Li12N,,0,S, cluster with a central Li,O, core, which comprises two parallel, six-membered Li,O, rings in their chair conformations (Figure l ) . [ ' *The cage structure consists of six pyramidal [0S(NtBu),l2-ions (mean bond angles: NSN 104.2(5)",[*] Prof.

{Li[P(NtBu)2]}4·0.25P4(NtBu)6: Solvent and Substituent Effects on the Structures and Reactivity of 1,3-Diaza-2-phosphaallyllithium Complexes

“…Cluster compounds have played an important role in the development of main group element chemistry . This topic has been enriched by recent studies of ternary systems containing homoleptic polyimido anions of the p-block elements, as their lithium derivatives. − In addition to the interest in the structures of these ternary clusters, and related quaternary systems, the polyimido anions themselves have been investigated as ligands that provide unusual environments for both main group , and transition metal centers. , …”

Syntheses and structures of an unsolvated tetrakisimidophosphate {Li3[P(NBut)3(NSiMe3)]}2 and the face-sharing double-cubane {Li2(THF)[P(O)(NBut)2(NHBut)]}2

“…7 The only example of a tetrakisimidophosphate was isolated in low yield as the solventseparated ion pair [Li(THF) 4 ] + [(THF) 2 Li(m-NR) 2 P(m-NR) 2 Li(THF) 2 ] 2 (R = naph) by the curious redox reaction between P 2 I 4 and Li 2 Nnaph (generated in situ) in THF/NEt 3 . 6 In connection with our interest in the structural consequences of the replacement of one (or more) of the imido groups in the anions of these clusters by an oxo ligand, 8 we wished to compare homoleptic [P(NR) 4 ] 32 systems with the isoelectronic, heteroleptic anions [OP(NR) 3 ] 32 . To this end we have developed a rational synthesis of tetrakisimidophosphates from the iminophosphoranes Me 3 SiNNP(NHR) 3 (1a, R = Bu t , 1b, R = Cy).…”

Assembly of a Heterobimetallic Diazasulfate Cluster via an Li4O4 Ladder

“…The structural consequences of replacing one or more of the NR groups attached to the p-block element in these ternary clusters by an isoelectronic oxo ligand are not readily predictable. In the only reported examples, dilithium derivatives of the heteroleptic imido/oxo dianions [OS(N t Bu)(NR)] 2- (R = t Bu, SiMe 3 ) were characterized as 36 atom (Li 12 S 6 O 6 N 12 ) clusters whose novel structures are generated by oligomerization of smaller units via their Li x O x face ( x = 2, R = t Bu; x = 3, R = SiMe 3 ) . Extension of this concept to quaternary systems involving the dianions [O 2 S(NR) x ] 2- ( x = 1, 2) evokes the possibility of extended structures formed by aggregation through two Li x O x faces of the fundamental unit .…”