Koordinationschemie perhalogenierter Cyclopentadiene und Alkine, X^[1] Darstellung und Molekülstruktur eines Cyclopentadienyl‐1,3‐dithiol‐π‐Komplexes, [C₅Cl₃(SH)₂]Mn(CO)₃

Abstract

Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, X[1]. – Synthesis and Molecular Structure of a Cyclopentadienyl‐1,3‐dithiol π Complex, [C5Cl3(SH)2]Mn(CO)3 The reaction of [C5Cl4Li]Mn(CO)3 with elemental sulfur leads to [C5Cl4SLi]Mn(CO)3 (1), which is easily oxidized by air to the disulfide (OC)3Mn[C5Cl4S–SCl4C5]Mn(CO)3 (2). Addition of one equivalent of BuLi, followed by an excess of S8 produces the dithiolate [C5Cl3(SLi)2]Mn(CO)3 (3), which yields the dithiol [C5Cl3(SH)2]Mn(CO)3 (5) upon hydrolysis. The molecular structures of 2 and 5 have been determined by X‐ray diffraction.

The Synthesis and Metal Coordination Chemistry of a Novel Phosphine- and Thiolate-Substituted Ferrocenediyl Ligand

“…The C−S distance of 1.761(7) Å is noticeably longer than that seen in other π-complexed C 5 and C 6 S−H substituted ring systems (ca. 1.72 Å), , there being no other structurally characterized examples of ferrocenyl S−H compounds; the only slightly similar structure to have been reported is a diphenylphosphinyl benzenethiol species [2-(Ph 2 PO)-6-(Me 3 Si)C 6 H 3 SH] . The angles at phosphorus are all significantly reduced from tetrahedral, ranging between 99.7(2) and 102.7(3) Å, the most “acute” angle being that subtended by the two phenyl rings.…”

“…The C-S distance of 1.761(7) Å is noticeably longer than that seen in other π-complexed C 5 and C 6 S-H substituted ring systems (ca. 1.72 Å), 16,17 18 The angles at phosphorus are all significantly reduced from tetrahedral, ranging between 99.7(2) and 102.7(3) Å, the most "acute" angle being that subtended by the two phenyl rings. As an investigation into its coordination chemistry, 2 was deprotonated (using n-butyllithium), treated with trans-[Pd(PhCN) 2 Cl 2 ] in toluene, and stirred at room temperature for 20 h. Following workup and crystallization in CH 2 Cl 2 -hexane (1:1), 3 was isolated as a brown microcrystalline powder in 64% yield, which analyzes as a bridged dimer species, with a structure seemingly analogous to the product formed with the previously reported 1-thiolate, 1′-(mesitylthio)ferrocene ligand; 12b that is, for each ligand in the Pd dimer, the thiolate S adopts a binucleating role.…”