Synthesis and characterization of a stable non-cyclic bis(amino)arsenium cation

Abstract

The reaction of Li[Mes*NH] (1, Mes* = 2,4,6-tri-tert-butylphenyl) with aminoarsane Mes*N(H)AsCl2 (2, Mes* = 2,4,6-t-Bu3C6H2) at −80 °C resulted in the formation of bisamino(chloro)arsane (Mes*NH)2AsCl (3Cl) by elimination of LiCl. 3Cl reacted with the Lewis acids such as AlCl3, GaCl3, and Ag[X] (X = AsF6−, OTf−, BF4−; OTf = trifluoromethanesulfonate = OSO2CF3−) upon chloride ion abstraction to give salts bearing the cation [(Mes*NH)2As]+ (3[X]; X = AsF6−, OTf−, BF4−, ECl4; E = Al, Ga). 3+ represents the first NH-functionalized acyclic bis(amino)arsenium cation. The formation of the salts bearing 3+ could also be observed in the reaction of cyclo-1,3-diarsa-2,4-diazane [ClAs(μ-NMes*)]2 (4) with Lewis acids (AlCl3, GaCl3) in the presence of proton sources in solution. All presented salts 3[X] were stable at room temperature and fully characterized.

Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements

“…The Schulz group reported the synthesis of a series of acyclic chloropnictenium and bisaminopnictenium cations (172)(173)(174)(175)(176) with amino group substituents by chloride abstraction. 386,[402][403][404][405][406] The amino group can enhance the stability of the electron deficient pnictenium center by p-donation from the nitrogen lone pair, but most of these species were not stable at room temperature in solution.…”

An Acyclic Arsenium Cation Stabilised by a Single P–As π‐Interaction and a Cyclic Diphosphinophosphonium Salt

“…The formally two‐coordinate arsacenium cation II was reported in 1983 by Jutzi and co‐workers, while Krossing and co‐workers subsequently reported the chloroarsacenium cation III . The poorly stable diaminoarsenium cation IV was reported by Schulz and co‐workers, and these authors have very recently isolated the room‐temperature‐stable diaminoarsenium salts [(Mes*NH) 2 As][X] ( V ) [X=AsF 6 , BF 4 , AlCl 4 , GaCl 4 ] . In addition, a very small number of related acyclic stibenium and bismuthenium cations have been reported…”

The New Complexes of Tris(2-Methoxy-5-Bromophenyl)Stibine with Silver Nitrate

“…В ИК-спектрах комплексов 1 и 2 присутствуют полосы, характеризующие колебания связей SbO, SbC, С≡N-и NO 3 -групп. Рентгеноструктурный анализ комплексов проводили на автоматическом четырехкружном дифрактометре D8 Quest Bruker (МоК α -излучение, λ = 0,71073 Å, графитовый монохроматор) при 293 К. Кристаллографические характеристики: 1  триклинная сингония, пространственная группа P-1, a = 9,32(3), b = 17,50 7, c = 17,97(5) Å,  = 97,56 (14), β = 92,90(19),  = 99,45(19) град., V = 2859(16) Å 3 , Z = 2,  выч = 2,069 г/см 3 ; 2  моноклинная сингония, пространственная группа С2/с, a = 17,417 (14), b = 21,041 (15), c = 32,01(2) Å,  = 90, β = 97,79(3),  = 90 град., V = 11624(15) Å 3 , Z = 4,  выч = 2,006 г/см 3 . В мономерной и димерной молекулах кристалла 1 нитратные лиганды являются хелатирующими и мостиковыми соответственно.…”

“…2,310 (14) C(41)Sb(2)C(31) 95,8(5) Ag(2)O (10) 2,517(15) C(51)Sb(2)Ag(2) 122,7(4) Ag(2)O (11) 2,528(16) C(51)Sb(2)C(31) 98,8(5) Ag(1)O 72,477(12) C(51)Sb(2)C(41) 99,2(5) Ag(1)O (8) 2,391 11 22,226 14N(3)Ag(2)O (10) 101,1(5) N(4)O 101,25(2) N(3)Ag(2)O (11) 82,1(6) N(4)O (11) 1,159 18O(10)Ag(2)Sb(2) 118,6(3) O(8)N 11,235 12O(10)Ag(2)O 1187,1(6) O(9)N 11,242 12O(11)Ag(2)Sb(2) 133,9(4) O 7N 11,229 12 212,130 7C(11)Sb(1)Ag(1) 119,08(19) Sb(1)C 112,123 7С(1)Sb(1)С 2198,2(3) Sb(2)Ag 22,5802(19) С(1)Sb(1)С (11) 98,4(3) Sb(2)C 412,124(8) С(11)Sb(1)С 2198,5(3) Sb(2)C 512,126 7C(41)Sb(2)Ag(2) 122,5(2) Sb(2)C 312,135 7C(51)Sb(2)Ag 2118,49(19) Ag(1)O 122,302(10) C(51)Sb(2)C(31) 99,9(3) Ag(2)O 9B2,529 14C(31)Sb(2)Ag(2) 114,6(2) Ag(2)O 9B 12,319 11Sb…”