Übergangsmetall‐substituierte Diphosphene, XX 1) Synthese und Eigenschaften des Tetrahedrans [(η 5 ‐C 5 Me 5 )(CO) 2 FeP–P t Bu]Fe 2 (CO) 6 und der metallierten 1,3‐Diphospha‐2‐propanone [(η 5 ‐C 5 Me 5 )(CO) 2 Fe–PC(O)–PR]Fe 2 (CO) 6 [R = t Bu, 2,4,6‐(CF 3 ) 3 C 6 H 2 ]

Transition‐Metal‐Substituted Diphosphenes, XX 1) . – Synthesis and Properties of the Tetrahedrane [(η 5 ‐C 5 Me 5 )(CO) 2 ‐FeP–P t Bu]Fe 2 (CO) 6 and the Metalated 1,3‐Diphospha‐2‐propanones [(η 5 ‐C 5 Me 5 )(CO) 2 Fe–PC(O)–PR]Fe 2 (CO) 6 [R = t Bu, 2,4,6‐(CF 3 ) 3 C 6 H 2 ] The reaction of [η 5 ‐C 5 Me 5 )(CO) 2 FeP(SiMe 3 ) 2 ( 1 ) with t BuPCl 2 ( 2a ) affords the metalated cyclotetraphosphane [(η 5 ‐C 5 Me 5 )‐(CO) 2 FeP–P t Bu] 2 ( 4a ) besides the metal‐substituted cyclotriphosphane (η 5 ‐C 5 Me 5 (CO) 2 Fe–P[P t Bu] 2 ( 5a ) and the diphosphane (η 5 ‐C 5 Me 5 )(CO) 2 FeP(SiMe 3 )P(Cl) t Bu ( 3a ), which are detected in the reaction mixture by 31 P‐NMR spectroscopy. Treatment of 4a with excess of Fe 2 (CO) 9 leads to the tetrahedrane [(η 5 ‐C 5 Me 5 )(CO) 2 FeP–P t Bu]Fe 2 (CO) 6 ( 6a ) and the 1,3‐diphospha‐2‐propanone derivative [(η 5 ‐C 5 Me 5 )(CO) 2 FePC(O)‐P– t Bu]Fe 2 (CO) 6 ( 7a ). Similarily, an analogous complex 7c is obtained from the reaction of in situ prepared (η 5 ‐C 5 Me 5 )‐(CO) 2 FePP–C 6 H 2 (CF 3 ) 3 ‐(2,4,6) with an excess of Fe 2 (CO) 9 .