Dimeric N-tert-butyl(chloroarsine)imine, C8H18As2Cl2N2

Abstract

[Zn(C7H4NOaS)E(HEO)4].2H20 AND [Cd(CTH4NO3S)E(H20)4].2H20molecule [0(4)] giving the shortest M-O distance involved in the shortest, and presumably strongest, intermolecular H-bonding. The orientation of the two C7H4NOaS ligands, which are basically coplanar, is such that the ligand planes are close to the plane containing the two nitrogens, the metal and the 0(4) oxygens. The dihedral angle between the two planes defined by the ligand ring atoms and the M, N and 0(4) atoms is ~16 °, and that between the ligand plane and the M,N,O(5) plane is ~72 °. Such an arrangement will place the lone pairs on the sp 2 N atoms approximately parallel to the M--O(5) bonds, and it is possible that these will exert some repulsive effect on the 0(5) water molecules leading to a weakening of these bonds. It is the M-O(5) bond that suffers Jahn-Teller elongation in the Cu complex, and in such distortions it is invariably the weakest bonds that are lengthened. The results of thermal studies of the seven hexahydrates (Haider, Malik & Wadsten, 1983) indicate that the energy of dehydration is minimum for the Cu complex and maximum for the Ni complex. All six H20 molecules are removed within 350-490 K. The energy of dehydration, which is related to the binding energy of the H20 molecules in the crystal, increases in the order Cu < Cd<Mn~Zn<Fe,--Co<Ni, and has values of 355. 8, 385.1, 418.6, 427.0, 594.4, 602.8 Introduction. Olah & Oswald (1960) prepared alkyl (chloroarsine)imines [RNAsC1],, from primary amines and arsenic trichloride; molecular weight measurements indicated n = 2 for R = tert-butyl, and n > 3 for other alkyl substituents. Vetter, Strametz & Nrth (1963) also prepared the tert-butyl derivative and proposed a dimeric structure. The crystal structure of the methyl analogue (Weiss & Eisenhuth, 1967) showed it to be trimeric with a six-membered [AsN] a ring. We report here the structure of [t-BuNAsC1] 2, prepared by a new route.

Syntheses and Structures of Heterobicyclic Bis(tert-butylamido)cyclodiphosph(III)azane Compounds Having Phosphorus(III) and Arsenic(III) Centers

“…As in 1, the element-chloride bond is elongated, 2.3325(11) Å, compared to those in [ClAs(µ-N t Bu) 2 AsCl] (2.250(3) Å). 21 With the completed characterization of 1 and 4, a homologous series of group 15 compounds of formula {[( t BuNP) 2 ( t BuN) 2 ]-ECl} now exists. Important bond parameters for the X-ray structurally characterized P, As, and Sb analogues are compared in Table 2.…”

Identification of new N–Sb topologies: understanding the sequential dehydrochloride coupling of primary amines and trichloropnictines

“…While specific examples of the consequential aminodichlorophosphines 2P, 5,6 diphosphinoamines 3P 6,7 and diaminophosphines 5P 5 have been isolated, the intramolecular dehydrochloride cyclization to 7P is highly favored and acyclic diphosphadiazanes, such as 6P have not been observed. Dehydrochloride coupling reactions have been reported for AsCl 3 8 and SbCl 3 , 9 but not for BiCl 3 , although reactions of alkali metal amides with PnCl 3 have been generally applied to prepare 2,4-substituted cyclo-2,4dipnicta-1,3-diazanes (Pn 5 As, [10][11][12][13][14] Pn 5 Sb, 9,14-22 Pn 5 Bi 14,22,23 ). Cyclotripnictatriazanes 8Pn are rare, [24][25][26] but recently we have realized that the presence of the medium sized substituents 2,6dimethylphenyl-(Dmp) or 2,6-diisopropylphenyl-(Dipp) at nitrogen facilitates transformation of the dimer 7 to the trimer 8 for Pn 5 P 27 or As.…”

“…We thank the Natural Sciences and Engineering Research Council of Canada, the Killam Foundation, the Canada Research Chairs Program, and the Sumner Foundation for funding. (5), 436 (9), 494 (14), 543 (11), 670 (13), 770(2), 769(3), 928 (11), 1027 (15), 1098 (12), 1139 (19), 1154 (20), 1211 (6), 1262 (7), 1577 (10), 1598 (8), 3295 (17), 3357 (16), 3374 (18); NMR: 1 H (CDCl 3 ): 2.18 (s), 3.86 (s), 6.69 (t), 6.94 (d); Crystal Data: C 24.5 H 34 Cl 7 N 3 Sb 2 , M 5 862.20 g mol 21 , triclinic, P-1, a 5 9.9556( 7 Isolation of 6Sb and 8Sb: DmpNH 2 (4.94 mL, 39.3 mmol) added to NEt 3 (5.71 mL, 39.6 mmol) and SbCl 3 (6.23 g, 27.3 mmol) in toluene (110 mL) at 0 uC, stirred for 1.5 h at RT. Filtered and the solvent was removed in vacuo to 5 mL, addition of pentane (5 mL) gave a yellow precipitate after 4 days at 224 uC, which was dissolved in minimal CH 2 Cl 2 and vapour diffusion of pentane gave a mixture of crystals (0.13 g) with two distinct morphologies and colours, manually separated.…”

“…Filtered and the solvent was removed in vacuo to 5 mL, addition of pentane (5 mL) gave a yellow precipitate after 4 days at 224 uC, which was dissolved in minimal CH 2 Cl 2 and vapour diffusion of pentane gave a mixture of crystals (0.13 g) with two distinct morphologies and colours, manually separated. Pale yellow (, 0.02 g) 6Sb; Crystal Data: 5), 325 (9), 373 (11), 486 (15), 522 (8), 690 (10), 707 (7), 790(3), 811(2), 839(4), 901 (16), 984 (12), 1023 (13), 1097 (6), 1164(1), 1252 (14), 1586 (17), 1799 (19), 1867 (20), 1934 (18); NMR: 1 H (CDCl 3 ): 2.60 (s, 3H), 2.66 (s, 6H), 2.69 (s, 3H), 2.74 (s, 6H), 7.02-7.17…”

“…10.4211(7) A ˚, c 5 16.9114(12) A ˚, a 5 85.8918(10)u, b 5 84.9494(10)u, c 5 73.7057(9)u, V 5 1675.5(2) A ˚3, T 5 193(2) K, Z 5 2, m(MoKa) 0.71073 (A ˚), Reflections; 6811 unique, 6180 observed, R (for 6180 reflections with (I . 2s(I))) 5 0.0220; wR(all) 5 0.0600.…”