Synthesis and characterization of thiolate, -amido, and -oxy heterocyclic-containing niobocene complexes: X-ray molecular studies of [Nb(η5-C5H4SiMe3)2(η2-N,S-S(C6H7N2))] (3)

Heterocycle-containing niobocene derivatives from hydride–niobocene complexes

“…This complex contains the same cation as the complex [Cp 0 2 Nb(CNXylyl) 2 ][HB(C 6 F 5 ) 3 ] reported by some of us [13] in an acid-base process involving 9 with B(C 6 F 5 ) 3 in the presence of CNXylyl. The geometry proposed for the structure of 15 (see Scheme 6) is consistent with the 1 H and 13 C NMR spectra of this complex.…”

“…13 , 98.1, 100.2, 103.9, 105.9 (C 2-5 , exact assignment not possible, C 5 H 4 SiMe 3 ), 120.3, 120.4 (C 5-6 aromatic system of bzta), 122.2, 126.6 (C 4-7 aromatic system of bzta), 128.2 (C 3 0 aromatic system of bzta), 142.2 (C 7 0 aromatic system of bzta), 173.7 (C 2 aromatic system of bzta).…”

“…For example, some aminopyridinato-containing complexes of groups 4 and 5 have been described [9]. Some of us have previously described examples of pyrimidinethiolate-containing zirconocenes [10], oxy and thiolate pyrimidine-containing Ti and Zr species [11], mercapto-containing Zr complexes [12] and, more recently, a series of thiolate, amido, and oxy heterocyclic-containing niobocene complexes [13]. As a continuation of our interest in the chemistry of hydride-niobocenes, we report here the reactivity of [Cp 0 2 Nb(H) 3 ] and [Cp 0 2 Nb(H)(CNXylyl)] towards new types of heterocycles functionalized with hydroxy, mercapto or amino groups.…”

New Monocyclopentadienyl Complexes of Tantalum(V) and Titanium(IV) with Chelating Pyrimidinethiolate and Oxypyridine Ligands − Molecular Structure of [Cp*TaCl3(SC6H7N2)]

“…[13] Finally, the Ta(1)ϪS (1)ϪC (1) angle [84.6(2)°] is in accordance with others observed in this kind of complexes. [10,11] When 3-cyano-2-hydroxy-4,6-dimethylpyridine was treated with [Cp*TaCl 4 ] in the presence of Et 3 N in toluene at room temperature [Equation (2)] complex 2 was isolated Figure 1. ORTEP drawing of complex 1 with the atomic labeling scheme; hydrogen atoms omitted for clarity; thermal ellipsoids are at the 30% level of probability (5) N (1)ϪTa (1)ϪCl (1) 76.2(1) Ta (1)ϪN (1) Ta (1)ϪCl (3) 2.393 (2) N (1)ϪTa (1)ϪCl (2) 76.3(2 Ta(1)ϪCl (2) 2.407(2) N(1)ϪTa(1)ϪCl(3) 87.6(1) Ta(1)ϪCl (1) 2.407(2) Cl(2)ϪTa(1)ϪCl(1) 151.37(8) Ta(1)ϪC (14) 2.431 (8) Cl ( (11) 2.447 (7) Cl ( (10) 2.472 (8) Cl (2)ϪTa (1)ϪS (1) 87.49(9) Ta(1)ϪC (12) 2.484 (7) Cl (3)ϪTa (1)ϪS (1) 151.96(7) C(1)ϪS(1)ϪTa (1) 84.6(2) C(1)ϪN(1)ϪTa (1) 99.5(4) C(4)ϪN(1)ϪTa (1) 143.8 (4) as a yellow, air-sensitive solid which was sparingly soluble in alkanes but soluble in toluene or THF.…”

“…[9] A systematic study of the chemistry of mono-and bis(cyclopentadienyl) complexes of group-4 transition metals bearing chelating pyrimidinethiolate ligands and analogous oxygen derivatives has been carried out by our research group in recent years. [10] The interesting coordination modes and the reactivity observed along with the scarce number of reported examples of this kind of compounds [11] encouraged us to prepare analogous monocyclopentadienyl complexes of group-5 metals. In particular, this paper will focus on the synthesis, structural details and reactivity of new monocyclopentadienyl complexes of tantalum() and titanium() bearing chelating pyrimidinethiolate and oxypyridine ligands.…”