Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)n(μ-H)(μ-PtBu2)(μ-Ph2PCH2PPh2)] (n = 4; 5) und [Ru2(CO)4(μ-CH2)(μ-H)(μ-PtBu2)(μ-Ph2PCH2PPh2)]

✍ Scribed by Hans-Christian Böttcher; Clemens Bruhn; Kurt Merzweiler

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: German
• Weight: 136 KB
• Volume: 625
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199904)625:4<586::aid-zaac586>3.0.co;2-b

✦ Synopsis

Inhaltsu È bersicht. Die Reaktion von [Ru 2 (l-CO)(CO) 5 (l-H)(l-P t Bu 2 )( t Bu 2 PH)] (2) mit dppm fu È hrt zum Zweikernkomplex [Ru 2 (l-CO)(CO) 4 (l-H)(l-P t Bu 2 )(l-dppm)] (3) (dppm = Ph 2 PCH 2 PPh 2 ). 3 spaltet thermolytisch oder durch Fotobestrahlung sehr leicht einen Carbonylliganden ab und liefert den entsprechenden elektronisch und koordinativ ungesa È ttigten Komplex [Ru 2 (CO) 4 (l-H)(l-P t Bu 2 )(l-dppm)] (4). 4 ist auch durch Eintopfsynthese aus [Ru 3 (CO) 12 ],

einem Ûberschuû an t Bu 2 PH und der sto È chiometrischen Menge dppm u È ber die Bildung von [Ru 2 (CO) 4 (l-H)(l-P t Bu 2 )( t Bu 2 PH) 2 ] (1) erha È ltlich. 4 weist eine Ru±Ru-Doppelbindung auf, die durch Addition von Methylen zum Dimetallacyclopropan [Ru 2 (CO) 4 (l-CH 2 )(l-H)(l-P t Bu 2 )(ldppm)] (5) nachgewiesen werden konnte. Die Moleku È lstrukturen von 3, 4 und 5 wurden durch Ro È ntgenkristallstrukturanalysen bestimmt.

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X-ray Crystal Structures of [Ru 2 (CO) n (l-H)(l-P t Bu 2 )(l-Ph 2 PCH 2 PPh 2 )] (n = 4; 5) and [Ru 2 (CO) 2) with dppm yields the dinuclear species [Ru 2 (l-CO)(CO) 4 (l-H)(l-P t Bu 2 )(l-dppm)] (3) (dppm = Ph 2 PCH 2 PPh 2 ). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru 2 (CO) 4 (l-H)(l-P t Bu 2 )(l-dppm)] (4). 4 is also obtainable by an one-pot synthesis from [Ru 3 (CO) 12 ], an excess of t Bu 2 PH and stoichiometric amounts of dppm via the formation of [Ru 2 (CO) 4 (l-H)(l-P t Bu 2 )( t Bu 2 PH) 2 ] (1). 4 exhibits a Ru±Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru 2 (CO) 4 (l-CH 2 )(l-H)(l-P t Bu 2 )(l-dppm)] ( 5). The molecular structures of 3, 4 and 5 were determined by X-ray crystal structure analyses.