Reactivity of Bis(3,5-dimethylpyrazol-1-yl)methyllithium with S or CS₂, Followed by Reaction with Fe₃(CO)₁₂ and Ar₃SnCl or RX: Unexpected Formation of (3,5-Dimethylpyrazol-1-yl)dithioformate Derivatives

Abstract

Reaction of bis(3,5-dimethylpyrazol-1-yl)methyllithium with sulfur at −70 °C, followed by reaction with Fe3(CO)12 and triaryltin chlorides, yielded trinuclear butterfly cluster complexes. When the triaryltin chlorides were replaced by organic halides, unexpected (3,5-dimethylpyrazol-1-yl)dithioformate derivatives were obtained. In addition, treatment of bis(3,5-dimethylpyrazol-1-yl)methane with n-BuLi at 0 °C resulted in partial decomposition to yield a carbene intermediate and a 3,5-dimethylpyrazolate anion. The carbene intermediate readily dimerized, and reaction of the anion with carbon disulfide, and subsequently with Fe3(CO)12 and organic halides, also gave the dithioformate derivatives.

Sn,P-Peri-Substituted Naphthalene as a Ligand for Transition Metals

“…The IR spectra of 2 and 3 showed eight (for 2 ) and seven (for 3 ) stretching vibrations of CO bonds in the range of ν = 2065–1815 cm –1 . This is consistent with the existence of ionic fragments [Mn­(CO) 4 ] + /[Mn­(CO) 5 ] − (ν = 2149–1843 cm –1 ) and [Co­(CO) 3 ] + /[Co­(CO) 4 ] − (ν = 2120–1859 cm –1 ). , The IR spectra of 4 – 6 showed stretching vibration of the CO bonds in the range of ν = 2060–1866 cm –1 , typical for Sn -coordinated M­(CO) n fragments …”

“…The Sn1–Fe1 bond distance [2.5383(6) Å] is close to the sum of the covalent radii of the individual atoms (Σ cov Fe,Sn = 2.56 Å), while the P1–Fe1 distance [4.0403(13) Å] is longer than Σ vdW P,Fe = 3.74 Å . The length of the Sn–Fe bond corresponds to the κ 1 Sn coordination of 1 but is somewhat longer than that of the related Sn → Fe coordinated complexes [2.408(1)–2.492(1) Å] . In 5 and 6 , the pentacoordinated central M1 atoms have a distorted trigonal bipyramidal geometry with τ = 0.55 for 5 (M1 = Fe, see Figure S2) and τ = 0.57 for 6 (M1 = Ru, Figure ).…”

(Pyrazol-1-yl)carbonyl and Ester-Functionalized Bis(pyrazol-1-yl)methide Carbonyl Tungsten Complexes

“…Furthermore, n -butanol appeared to promote the formation of the 3,5-dimethylpyrazolate anion, and the addition of a small quantity of n -butanol to the reaction mixture led to significant improvements in the yields of 3 and 4 . Taken together with our previous finding that a 3,5-dimethylpyrazolate anion was generated during the formation and subsequent reaction of a bis(3,5-dimethylpyrazol-1-yl)methyl anion, and the fact that lithium n -butoxide is formed by the oxidation of n -BuLi with oxygen, these results led to the construction of a plausible pathway for the formation of 3 and 4 , which is depicted in Scheme .…”

“…In contrast, the treatment of these acylmetalates with a soft electrophile results in the formation of metal–acyl complexes . As part of our ongoing interest in the reactivity of bis(pyrazol-1-yl)methide anion, we herein report the reaction of bis(pyrazol-1-yl)methyllithium with tungsten carbonyl, followed by the reaction of the resulting intermediate with iodine, which yielded unexpected (pyrazol-1-yl)carbonyl and ester-functionalized bis(pyrazol-1-yl)methide tungsten derivatives, together with bis(pyrazol-1-yl)acyl tungsten complexes.…”

Synthesis and Characterization of a Thiopyridazinylmethane-Based Scorpionate Ligand: Formation of Zinc Complexes and Rearrangement Reaction

“…A literature search for similar complexes reveals that the molecular structures of 3b , c display a rare class of methanido complexes where different heteroatoms are bound to the central methanide carbon atom. Thus, complex 3b reveals the first crystallographically characterized C–N,N,S -methanido complex and for complex 3c only four other C–N,S,S- methanido complexes are known. ,,, Furthermore, mononuclear zinc carboxylate complexes featuring an alkyl group are also rare, as only 13 structurally characterized complexes are known, of which most zinc centers are tetrahedrally coordinated bearing a monodentate carboxylate. Therefore, only two carboxylate complexes with bidentate coordination , and three complexes with a trigonal-bipyramidal , or a distorted-octahedral geometry are present.…”