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Reactions of the low valent azido complex NEt 4 [CpMn(CO) 2 N 3 ] (1) with electrophiles preferably give the dinitrogen complex [CpMn(CO) 2 N 2 ] (2). Thus, 2 forms when 1 is reacted with NOBF 4 , NO 2 BF 4  or HCl/THF. respectively. 2 forms also if 1 is reacted with the 1,3-dipolarophile CI 3 C-CN. The reaction of 1 with CH 3 I. however, gives the methylamine complex [CpMn(CO) 2 NH 2 CH 3 ], presumably via methylazido, -nitrene and -aminyl interm ediates. Cycloadditions could be achieved with the isoelectronic [CpFe(cdpe)N 3 ] (3); 3 yields the corresponding 2-triazolato-4,5-dialkylester complexes 4 when reacted with RO 2 C-C=C-CO 2 R(4a: R = Me; 4b: R = Et). The ethyl derivative was characterized by X-ray structure analysis.

zeitschrift für naturforschung b

Reaktionen an komplexgebundenen Liganden, XXXIX.  Reaktionen der niedrigvalenten Azido-Komplexe NEt 4 [CpMn(CO) 2 N 3 ] und [CpFe(cdpe)N 3 ] mit Elektrophilen und 1,3-DipolarophiIen (cdpe = cis-1,2-Bis(diphenylphosphino)ethen) / Reactions of Complex Bound Ligands, XXXIX. Reactions of the Low Valent Azido Complexes NEt 4 [CpMn(CO) 2 N 3 ] and [CpFe(cdpe)N 3 ] with Electrophiles and 1,3-Dipolarophiles (cdpe = cis-1,2-Bis(diphenylphosphino)ethen)