John H. Matonic

Divalent metal chloride formamidine complexes, M11 = Fe, Co and Pt. syntheses and structural characterization

Abstract The reactions of anhydrous FeCl2, CoCl2 and K2PtCl4 with N,N′-di(p-tolyl)-formamidine (HDTolF) yield crystalline materials which are soluble in common organic solvents. FeCl2(HDTolF)2 (I) and CoCl2(HDTolF)2 (II) have a pseudo-tetrahedral coordination about the metal centre, while [PtCl(HDTolF)3]Cl (III) has a square-planar arrangement of atoms around the platinum atom. The latter reacts with butyllithium to produce PtCl(DTolF) (HDTolF)2 (IV). All compounds reported have been characterized by X-ray crystallography and by various spectroscopic techniques. The facility with which they formand the high purity in which they are isolated, as well as their favourable solubility characteristics, make them attractive starting materials for the preparation of other formamidinato complexes.

An unusual complex derived from MoCl3(THF)3 and AgBF4 in acetonitrile : synthesis and structure of [Mo2(μ-F)(NCCH3)8O2[BF4]3

Abstract Reaction of MoCl 3 (THF) 3 with 3 equiv of AgBF 4 in refluxing acetonitrile produces the unusual solvated Mo IV -oxo complex [Mo 2 (μ-F)(NCCH 3 ) 8 O 2 [BF 4 ] 3 ( 1 ) as a result of oxidation by silver(I), as well as abstraction of both a fluoride ion from [BF 4 ] − and an oxygen atom from THF or adventitious water. Compound 1 has been investigated by 1 H and 19 F NMR, IR and UV-vis spectroscopy, electrochemistry and X-ray crystallography. Single crystal X-ray data collected at − 92 ± 2°C revealed that 1 is monoclinic, space group P 2/ n with a = 11.776(4), b = 12.293(7), c = 12.497(7) A, β = 100.90(4)°, V = 1776(1) A 3 and Z = 2. Final refinement led to R = 0.038 and R w = 0.059. The structural core of the molecule consists of the unusual group [OMoFMoO] 3+ for which the angle MoFMo is 165.0°. The pyramidal MoN 4 units around each molybdenum(IV) centre are staggered with respect to one another, and as a result of the basal N plane being 0.27 A from the molybdenum centre, the acetonitriles are canted towards the centre of the molecule forming a “cupped” central region around the bridging fluorine atom. This fluoride-bridged structure is unique among molybdenum(IV) dimers, and is one of only several documented examples in molybdenum chemistry.