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Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis Acceptors

“…The greater atomicr adii of the heavierp nictogen centers facilitates increasingly high coordination numbers, such that derivatives of Ph 4 SbX (X = halide) are molecular in the solid state and contain penta-coordinate, trigonal-bipyramidal Sb centers (Scheme 1c). [20][21][22] Nevertheless, only one complex [Ph 4 Sb(dmso)][PdCl 3 (dmso)] (Scheme 1d), [8] containing ap rototypical stibonium acceptor has been structurally characterized, along with the recent spectroscopic characterization of [(C 6 F 5 ) 4 Sb(OPEt 3 )][B(C 6 F 5 ) 4 ]. [14] We now report, therefore, the preparation and characterization of Ph 4 Sb(OTf) (1a)a nd Ph 3 Sb(OTf) 2 (3), and the systematic exploration of their interaction with classical ligands, evolvingo ur preliminary results for compound 3, [3] and establishing ap otentially diverse and extensivec oordination chemistry for cationic Sb V centers with implications for other heavy elements of the pblock.…”

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

“…With this chloride as an additional ligand, the antimony center adopts a trigonal bipyramidal geometry (AE](C-Sb-C) = 355.8(4)8) with a Sb-Cl distance (2.6835(9) ) very close to that of 2.668(1) found in Ph 4 SbCl. [7] Venanzi and Dawson had reported a complex of similar composition to that of 2, but with the chloride dissociated from the antimony center. [8] We believe that this species was in fact complex 2 whose structure had been misassigned.…”

The structure of tetraarylantimony halides and tetraphenylantimony isothiocyanate

“…Some tetraorganylantimony halides with halogen atom in the axial position were found to have trigonalbipyramidal structures [1][2][3][4][5][6][7]. The Sb-Hal bond length observed experimentally exceeds, as a rule, a sum of the covalent radii of the corresponding atoms.…”