Proton-induced reactivities of ruthenium azido complexes: the first example of boron-carbon bond formation by methylene insertion into a B-H bond.

Whereas the reaction of Tp(PhCN)(PPh(3))Ru-N(3) {Tp = HB(pz)(3), pz = pyrazolyl} with CH(3)I in CH(2)Cl(2) led to the cationic ruthenium methyleneimine complex [Tp(PPh(3))(PhCN)Ru(NH=CH(2))]I, the analogous reaction with HCl gave rise to the ruthenium chloride complex containing a methyl tris(pyrazolyl)borate ligand (Me)Tp(PPh(3))(PhCN)RuCl, as a result of the highly unusual methylene insertion into a B-H bond of the Tp ligand.

Chlorido[hydridotris(pyrazol-1-yl-κN)borato](1H-pyrazole-κN)(triphenyl-phosphine-κP)ruthenium(II).

In the title compound, [Ru(C(9)H(10)BN(6))Cl(C(3)H(4)N(2))(C(18)H(15)P)], the Ru(II) atom is coordinated by an N,N',N''-tridentate hydrido-trispyrazolylborate (Tp) ligand, a pyrazole (HPz) mol-ecule, a chloride ion and a triphenyl-phosphine ligand, resulting in a distorted RuClPN(4) octa-hedral coordination for the metal ion: the tridentate N atoms occupy one octa-hedral face and the Cl and P atoms are cis. One of the phenyl rings is disordered over two orientations in a 0.547 (10):0.453 (10) ratio, and a weak intra-molecular N-H⋯Cl hydrogen bond generates an S(5) ring.

Azido-(benzonitrile-κN)[hydrido-tris(pyrazol-1-yl-κN)borato](triphenyl-phosphine-κP)ruthenium(II).

Facile ligand substitution is observed when the ruthenium-azide complex, [RuN(3)(Tp)(PPh(3))(2)] [Tp,HB(pz)(3), pz = pyrazol-yl, PPh(3) = triphenyl-phosphine] is treated with benzo-nitrile, yielding the title compound, [Ru(C(9)H(10)BN(6))(N(3))(C(7)H(5)N)(C(18)H(15)P)]. The asymmetric unit contains two crystallographically independent mol-ecules. In each one, the Ru(II) atom is six-coordinated in a distorted octa-hedral geometry by five N atoms from an htpb ligand, an azide ligand and a benzonitrile ligand and one P atom from a triphenyl-phosphine (tpp) ligand. The azide group is almost linear and is coordinated to Ru with an average Ru-N-N angle of 124.9 (3)°.