Syntheses and structures of cyclopentadienyl arsenic compounds II. Pentamethyl- and tetraisopropylcyclopentadienyl arsenic amido derivatives

Chemistry of pnictogen(iii)–nitrogen ring systems

“…11,12 Interestingly, the tetramer [Cp*As(m-NH)] 4 , a rare example of a cyclotetrapnict(III)azane, is generated from the reaction of Cp*AsCl 2 and ammonia in diethyl ether. 13 The reaction of methylamine with Cp9AsX 2 (X = Cl, I) produces the cyclopentadienyl derivatives [Cp9As(m-NR)] 2 (5a and 5b) respectively. 13 However, when tert-butylamine is reacted with Cp*AsCl 2 , only the monomeric compound Cp*AsCl(NH t Bu) is obtained.…”

X-(Diiodoarsanyl)benzoic acid (X= 3 and 4)

“…Organoarsenic (As III ) halogenides are easily accessible compounds of the type R n AsHal 3Àn (n = 1, 2) and are widely used for the preparation of various organoarsenic derivatives (Gross et al, 1997), including arsa-heterocycles (Matuska et al, 2010;Avtomonov et al, 1997), diarsenes (Twamley et al, 1999), and organometallic complexes such as arsinidenes (Huttner & Evertz, 1986;Jutzi & Kroos, 1990) and cluster compounds (Song et al, 2001;Deck & Vahrenkamp, 1991;Deck et al, 1987). Iodine derivatives, with the I atoms as good leaving groups, have been shown to be particularly good reagents for introducing the RAs group into cluster complexes as a result of nucleophilic substitution reactions (Konchenko et al, 1999;Pushkarevsky et al, 2006;Winter et al, 1983;Ilyin et al, 2012).…”

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…”