The first evidence for a transient stibaallene ArSbCCR2

Hypervalent diorganoantimony(iii) fluorides via diorganoantimony(iii) cations – a general method of synthesis

“…By contrast, in the crystal of 6 a 3D architecture is formed based on weak C-H/p (Ar centroid ) contacts between parallel chain polymers of alternating (C Sb )-6 and (A Sb )-6 isomers connected through F(1)/H(7b) imine (2.31 Å) interactions. Surprisingly, no intermolecular F/H contacts are present in the crystal of 8; in this case a dimer association of (C Sb )(pS N1 )-8 and (A Sb )(pR N1 )-8 isomers is formed through C(7)-H(7B) methylene /Ar centroid {C(10 0 )-C(15 0 )} (2.99 Å; g ¼ 17.7 ) contacts and these dimer units are further associated into a layer based on C(11)-H (11) aryl /Ar centroid {C(10 0 a)-C(15 0 a)} (3.02 Å; g ¼ 13.7 ) contacts.…”

“…[1][2][3][4][5][6] A survey of the literature concerning organoantimony(III) uorides revealed some interesting aspects with regard to the preparation of the few R 2 SbF 7-12 and RSbF 2 (ref. [11][12][13][14] species reported so far. In earlier works [NH 4 ] 2 [PhSiF 5 ] was used for phenylation of SbF 3 in aqueous solution to give Ph 2 SbF.…”

“…8 However, the uorination was effective when the dibenzoazastibocine chloride MeN(CH 2 C 6 H 4 ) 2 SbCl was reacted with KF in DMF solution. 9 While the partial phenylation of SbF 3 with PhLi or PhMgBr reagents failed, the isolated product always being Ph 3 Sb regardless of the molar ratio of the reagents used, 8 for other organolithium reagents the reaction with SbF 3 led to the desired organoantimony(III) uorides, [10][11][12] even if the stoichiometry could not be fully controlled and from the reaction mixture both R 2 SbF and RSbF 2 were isolated by fractional crystallization, e.g. for R ¼ 2,4,6-t Bu 3 C 6 H 2 .…”

“…for R ¼ 2,4,6-t Bu 3 C 6 H 2 . 11,12 Taking into account the ability of the organoantimony(V) cations to react with the uoride anions we have decided to investigate the possibility to prepare diorganoantimony(III) uorides using ionic species such as the diorganoantimony(III) cation, [R 2 Sb] + . Monocations of this type can be stabilized by intermolecular [19][20][21][22][23][24] We report herein a new route for the preparation of the diorganoantimony(III) uorides via ionic diorganoantimony(III) derivatives stabilized by (C,N)-chelating ligands as well as their structural characterization both in solution and in the solid state.…”

Group 14 and 15 Heteroallenes ECC and ECE‘

“…In order to compare the stability of stibaallenes -SbdCd C< with that of their phosphorus 44 and arsenic 60 analogues, we planned to prepare Mes*SbdCdCR 2 61 with the same supermesityl group on antimony and including the terminal carbon atom in the fluorenylidene group. Arsaallene 60 was prepared by a route involving the initial formation of the AsdC double bond, which was successful, owing to the good stability of this bond.…”