Complexes of Stiboranium Mono‐, Di‐, and Trications

Abstract

Reaction of Ph SbCl with 2,2'-bipyridine and Me SiOSO CF releases chlorobenzene, which is interpreted as a reductive (Sb /Sb ) elimination from a complex of a stiboranium cation. Conversely, reactions of Ph SbCl with 4-methylpyridine-N-oxide and AgOSO CF give redox-resistant complexes with the generic formulae [Ph SbCl L ][OTf] , including a compound containing a pnictogen(V) trication.

Tris(benzoimidazol)amine (L) complexes of pnictogen(iii) and pnictogen(v) cations and assessment of the [LP]3+/[LPF2]3+ redox couple

“…Oxidation of [P(BIMEt 3 )][OTf] 3 by XeF 2 gives [PF 2 (BIMEt 3 )][OTf] 3 , containing a rare example of a cationic complex of the high oxidation state Pn( v ) center. 10 Previous examples include derivatives of [PnPh 3 L x ][OTf] 2 (L = pyridine N-oxide and Pn = As, 11 Sb, Bi 12 ) and [SbPh 2 L x ][OTf] 3 (L = pyridine N-oxide 13 ). …”

Photoreductive Elimination of PhCl Across the Dinuclear Core of a [GePt]VI Complex

“…Although oxidative addition of aryl chlorides on transition metal centers has been heavily investigated within the context of cross-coupling chemistry, 14 the reverse of this fundamental reaction, namely, the reductive elimination of aryl chlorides is of little precedence. Notable examples include the reductive elimination of chlorobenzene from Ph 2 SbCl 3 upon treatment with 2,2′-bipyridine and TMSOTf (Figure 7, I) as reported by Burford et al, 15 and the photoreductive elimination of C 6 F 5 Cl from a Au(III)-carbene complex bearing two chlorides and a pentafluorophenyl ligand (Figure 7, II) as reported by Rosenthal et al 16,17 The latter example is especially interesting in that, contrary to our system, the photoelimination of C 6 F 5 Cl does not appear to compete with the elimination of a Cl 2 equivalent. Related aryl-chloride eliminations have also been observed upon thermolysis of arylated phosphine gold(III) chloride complexes 18 such as Ph 3 PAuCl(CF 3 )(p-FC 6 H 4 ) (Figure 7, III).…”

Isolation and Structural Determination of a Hexacoordinated Antimony(V) Dication

“…Recently, advances have been made in the application of p‐block polycations as new Lewis superacids or as transition‐metal‐free catalysts due to their electrophilic properties [2, 3] . However, despite the fact that group‐15 elements (pnictogens, Pn) offer easy access to various oxidation numbers, examples of polycations that consist of group‐15 elements are rarer than those that consist of group‐13 (triels, Tr), group‐14 (tetrels, Tet), or group‐16 (chalcogens, Ch) elements [4–14] …”

“…[2,3] However,d espite the fact that group-15 elements (pnictogens, Pn) offer easy access to various oxidation numbers, examples of polycations that consist of group-15 elements are rarer than those that consist of group-13 (triels, Tr), group-14 (tetrels, Tet), or group-16 (chalcogens, Ch) elements. [4][5][6][7][8][9][10][11][12][13][14] Of the currently known pnictogen polycationics pecies, tricoordinated Pn V dications of the type[ R 3 Pn] 2 + (Pn = N, P, As, Sb, Bi)h ave recently attracteds ubstantial attention (Figure 1). [14][15][16] [R 3 Pn] 2 + are known as "pnictinyl dications" and can be formed by the formal removal of al one pair (LP) of electrons from the central atom of at rivalentp nictine( R 3 Pn).…”

“…Figure 2e). [10,28] We have recently reported the synthesis of the neutral stibine [(ppy) 3 Sb] (1), [32] which contains three 2-(2-pyridyl)phenyl (ppy) pendant-arm ligands. [33,34] Single-crystal X-ray diffraction analysiso f1 revealed a( pseudo-)hexacoordinateda nd distorted octahedral coordinationg eometry.T he three ppy pyridine moieties in 1 coordinate weakly to the centrala ntimony atom in an unsymmetrical facial configuration.T he structure of 1 and theoretical calculations suggest that the LP of each central antimony atom remains present without participating in the three intramolecular interactions.…”