Dioxygen activation by enzymes containing binuclear non-heme iron clusters

The Transition Metal Coordination Chemistry of Hemilabile Ligands

Bidendate ligands have proven important in a variety of complexes and are invaluable in a number of catalytic processes. While ligands of this type usually have two identical ligand fragments (homobidendate ligands), heterobidendate ligands allow for a differentiation of the ligands and therefore are prone to selective reactions. This is especially interesting in cases where the ligands are rather different from one another. Phosphane and cyclopentadienyl ligands are among the most commonly used in organometallic chemistry, and they are quite different in nature: Whereas a phosphane is electroneutral and often subjected to ligand exchange processes, the cyclopentadienyl ligand is normally considered to be negatively charged and rather tightly bound to a metal. Reviewing the literature in the field of cyclopentadienylmetal complexes bearing pendant phosphorus, arsenic, and sulfur ligands is timely given that the number of publications of relevance to this topic is growing exponentially as can easily be seen from the list of references in this review: the number of references since 1993 clearly exceeds that of all years before. The reason for this development may be that cyclopentadienylmetal complexes bearing pendant phosphorus, arsenic, and sulfur ligands are expected to perform chemistry different from that of usual cyclopentadienyl complexes. Indeed this has often been the case. Complexes discussed in this review facilitate the complexation of sensitive ligands, offer new aspects concerning chirality, allow novel reactions, and are beginning to be applied to transition metal catalysis. It is therefore hoped that this review will contribute to these developments by offering state of the art information for those active in the field and, even more important, for those who join in the future. This review covers the chemistry of cyclopentadienylmetal complexes, in which the cyclopentadienyl ligand bears a sidearm which includes a phosphorus, arsenic, or sulfur ligand. The pendant ligand has to be separated from the cyclopentadienyl part, that is, † Dedicated to Professor Günther Wilke on the occasion of his 75th birthday. * To whom correspondence should be addressed. Fax: +49/(0)511/ 762-4616. E-mail: holger.butenschoen@mbox.oci.uni-hannover.de. Holger Butenschön was born and raised in Hamburg, Germany. After his army service he studied chemistry at the University of Hamburg and obtained his Dr. rer. nat. degree in 1983 with Professor Armin de Meijere as a fellow of the Studienstiftung des Deutschen Volkes. From 1983 to 1984 he spent a postdoctoral year with Professor K. Peter C. Vollhardt at the University of California at Berkeley as a NATO fellow. Having returned to Germany, he joined the Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr as a Liebig fellow to do preparative organometallic work in the fields of anellated arenechromium complexes and cyclopentadienyl cobalt complexes with pendant phosphane ligands. After his habilitation in 1991 (University of Hamburg), he became a Heisenberg fellow of the DFG at the University of Wuppertal from 1992 to 1993. Since 1993 he has been a professor of organic chemistry at the University of Hannover. In 1999 he was a foreign visiting professor at Kyushu University in Fukuoka, Japan. Holger Butenschön is the editor of the German translation of Peter Vollhardt’s and Neil Schore’s textbook Organic Chemistry as well as a coauthor of the Memofix OC. He currently serves as the chairman of the Hannover district of the German Chemical Society (GDCh). His spare time is occupied by the female part of his family, his wife Bettina and their four daughters Lisa, Nora, Inga, and Lara. 1527 Chem. Rev. 2000, 100, 1527−1564

Cyclopentadienylmetal complexes bearing pendant phosphorus, arsenic, and sulfur ligands.

Coordination chemistry of heavy polychalcogenide ligands

Highly active catalyst systems for the ring-opening metathesis polymerization (ROMP) of strained (norbornene) and low-strain (cyclooctene) olefins are readily prepared from RuCl2(arene)(PR3) precursors (directly available by addition of a phosphine to the stable [(arene)RuCl2]2 dimers) after activation with (trimethylsilyl)diazomethane. Durene or p-cymene as arene ligands, together with a sterically demanding basic phosphine (typically tricyclohexylphosphine), promoted the formation of the most active polymerization catalysts. The effects of arene and phosphine ligands and of the solvent on polynorbornene and polyoctenamer molecular weight distributions and microstructures were investigated. The excellent functional group compatibility of the catalyst system was illustrated by the synthesis of a variety of polyoctenamers bearing epoxide, acid, ether, ester, acetal, and bromine functionalities. The polymers were isolated in quite good yields. The striking positional influence of the functional group on the...

Novel Ruthenium-Based Catalyst Systems for the Ring-Opening Metathesis Polymerization of Low-Strain Cyclic Olefins

The electron-rich metallothiol CpRu(PPh 3 ) 2 SH (1) has been prepared from the reactions of CpRu(PPh 3 ) 2 Cl with NaSH and CpRu(PPh 3 ) 2 H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh 3 )(CO)SH whereas the carbonylation of CpRu(PPh 3 ) 2 Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh 3 ) 2 (SH 2 )] + . Alkylation of 1 gives thiol complexes [CpRu(PPh 3 ) 2 (RSH)] + (R=CH 3 )

Interconversion of persulfido, sulfur hydride, and hydride ligands coordinated to CpRu(PPh3)2+

Synthesis, structure, and properties of [CpRu(PR3)2]2(μ-S2)2+. Effects of strong π-donation in a disulfur complex

Nonclassical polysulfide complexes: cage and ring compounds [(MeCp)Ru(PPh3)]2Sx (x = 6, 4)

Synthesis and structure of [CpRu(PPh3)2(SC2H4)]OSO2CF3. A transition-metal analogue of an episulfonium salt

Intramolecular dynamics in the mixed valence cluster (CH3C5H4)4Ru4S42+ : observation of mobile metal-metal bonds

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