Zirconium Alkyl Thiolate Complexes:  Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Abstract

The thiolate−alkylzirconocene complex Cp2ZrMe(SR) (2) (Cp = η5-C5H5; SR = 4,6-dimethylpyrimidine-2-thiolate) can be prepared by reacting the corresponding dialkylmetallocene complex Cp2ZrMe2 (1) with 1 equiv of 4,6-dimethyl-2-mercaptopyrimidine. X-ray structure analysis of complex 2 revealed that the thiolate group is bonded in an η2 fashion through the sulfur and one of the nitrogen atoms. Complex 2 reacts with 2,6-dimethylphenyl isocyanide (CNXylyl) to yield the corresponding iminoacyl derivative, Cp2Zr(η2-MeCNXylyl)(SR) (4). The molecular structure of 4 shows that the thiolate group is η1-bonded while the iminoacyl group behaves as a bidentate ligand. Reaction of compound 2 with different acidic reagents gives formation of methane and different zirconium complexes. Reaction with HSR renders Cp2Zr(SR)2 (3) and with (NHEt3)(BPh4) the cationic complex [Cp2Zr(SR)][BPh4] (5). An hydride thiolate complex, Cp*2ZrH(SR) (Cp* = η5-C5Me5) (6) can also be prepared by reaction of “Cp*2Zr” with HSR by an oxidative addition reaction.

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.…”

Heterocycle-containing niobocene derivatives from hydride–niobocene complexes

“…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.…”

Diastereoselective Insertion of Isocyanide into the Alkyl−Metal Bond of Methylbenz[e]indenyl ansa‐Zirconocene Complexes

“…[21,36] However the zirconium-nitrogen bond length [ZrϪN 2.2872(16) Å ] is slightly longer than those found in related zirconium iminoacyl compounds in the range 2.148Ϫ2.250Å . [37,38] The double bond character of the iminoacyl C(10)ϪN bond is confirmed by the 1.281(3) Å distance, which is longer than usual for related zirconium iminoacyl compounds and close to that known for organic CϭN bonds [1.28Å ].…”