Cyclopropene als Komplexliganden: Darstellung und Struktur von Komplexen des Typs (η³:η¹‐Allylcarbonyl)tricarbonyleisen, (η³:η¹‐C₃R¹R²R³R^3′CO)Fe(CO)₃, und Hexacarbonyl‐μ‐(phenylallyl)‐dieisen(FeFe), (C₃PhR¹R²R³)Fe₂(CO)₆

Abstract

Cyclopropene (la-e) reagieren mit Fe,(CO), im Molverhaltnis 1 : 1 unter Offnung des Dreirings und CO-Einschiebung zu (q : q '-Allylcarbony1)tricarbonyleisen-Komplexen (2 a -e). Die Struktur von Tricarbonyl(q3: q '-1,2,3-triphenylallylcarbonyl)eisen (2d) wurde rontgenographisch bestimmt. -3-Phenylsubstituierte Cyclopropene ( I d -f) reagieren mit iiberschiissigem Fe,(CO), zu Hexacarbonyl-p-(q2-phenyl-q3: q '-ally1)-dieisen(Fe -Fe)-Komplexen (4d -f). 4d und e entstehen auch aus 2d und e mit weiterem Fe,(CO),. Die Kristallstruktur von Hexacarbonylp-(I q2,2,3-triphenyl-q3 :q '-al1yl)-dieisen(Fe -Fe) (4d) wurde gleichfalls ermittelt. Cyclopropenes (la-e) react with Fe,(CO), in the molar ratio 1 : 1 to give (q3:q1-allylcarbonyl)-tricarbonyliron compounds (2a-e) with opening of the three-membered ring and insertion of CO. The structure of tricarbonyl(q3: q '-1,2,3-triphenylallylcarbonyl)iron (2d) has been determined by X-ray analysis. -3-Phenyl-substituted cyclopropenes (Id -f) react with excess Fe,(CO), to give hexacarbonyl-p-(q2-phenyl-q3 : q '-allyl)diiron(Fe -Fe) complexes (4d -f). 4d and e are also formed from2d and e with additional Fe,(CO),. The crystal structure of hexacarbonylp-( 1 q 2,2,3-triphenyl-q3 : q '-ally1)-diiron(Fe -Fe) (4d) has also been determined. Cyclopropenes as Complex Ligands

Migration of a phenyl group from co-ordinated CH2(PPh2)2 to an acetylide on an Ru3 cluster: crystal structure of [Ru3(μ-H)(μ3-PPhCH2PPh2)(μ3-PhC2But)(CO)6] †

“…16 Comparable "side-on" M-C interactions involving a double bond of the phenyl ring have been previously encountered in electron-deficient metal complexes such as [Fe 2 (µ-C 3 Ph 3 H)(CO) 6 ], 17 [Fe 2 {µ-C(OEt)CPhCHPh}-(CO) 6 ] 18 or [Fe 2 (µ-CHCHCMePh)(CO) 6 ]. 19 Analogously to these complexes, this interaction in 6 induces a partial localization of the C-C bonds of the phenyl ring, which become alternatively short and long (see Table 1). Such a "side-on" M-C interaction is different from those involving co-ordination between a metal center and a C-C (Ph) bond, as found in…”

Reaction of (1-3-.eta.-vinylcarbene)iron complexes with enneacarbonyldiiron. Formation of a (ferracyclopentadiene)iron (Fe-Fe) complex and a vinylcarbenediiron (Fe-Fe) complex

“…0.28 X 0.28 X 0.25 mm was used for X-ray data collection on the diffractometer. Integrated intensities were collected at 21 °C up to 55 °C in 20 by the 0-20 continuous scan mode at a 0 scan rate of 2°min"1 with graphite-monochromated Mo Ka radiation. Stationary background counts of 10-s duration were made on either side of the scan.…”

Reaction of a (π-Vinylcarbene)iron Complex with Tricarbonyl(η4-1,5-cyclooctadiene)ruthenium. Preparation, Structure, and Reactivity of Novel (μ-Vinylcarbene)(Fe−Ru) Complexes

“…General Discussion. As for the preparation of the homobinuclear vinylcarbene complex, the following representative methods are reported: (1) reaction of a binuclear carbonyl complex with cyclopropene derivatives; (2) reaction of a binuclear (μ-methylene)M 2 complex with acetylenes; (3) reaction of a (μ-acetylene)M 2 complex with diazomethane; (4) reaction of a mononuclear η 1 -vinylcarbene complex with metal carbonyls; , (5) activation of a C−H bond of an η 3 -allyl ligand …”

“…For the past two decades, much attention has been focused on the chemistry of mononuclear 1 − and binuclear transition-metal vinylcarbene complexes 2 , (η 4 -metallabutadiene)metal complexes 2 ‘, or η 3 :η 1 -allylidene complexes 2 ‘‘ (Chart ). − Especially, heterobinuclear vinylcarbene complexes − are of interest; however, methods of preparation of these complexes are not completely established. As for the preparation of (μ-vinylcarbene)(M 1 −M 2 ) complexes, the following two representative methods are reported: (1) reaction of (μ-methylene)(M 1 −M 2 ) 3 with alkynes (eq 1); (2) reaction of (η 1 -vinylcarbene)M 1 or 1-metallabutadiene 4 with M 2 (eq 2) .…”