the amine group is a part, disallow this. Thus, the observed N-H-Cl angle is only 138 (3)°.
ConclusionsA number of new five-coordinate ruthenium amide complexes have been prepared, all incorporating the tridentate "N(SiMe2CH2PPh2)2. The complex RuCl-(PPh3)[N(SiMe2CH2PPh2)2] (1) displays some unique reactivity patterns. Especially noteworthy is the conversion of the amide linkage of 1 to an amine via two distinct pathways: addition of H2 to produce the isomeric amine chlorides RuCl(PPh3)H[NH(SiMe2CH2PPh2)2] (2a,b) and activation of an ortho C-H bond of the PPh3 unit to generate RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2] (4). The driving force for both of these reactions appears to be the formation of an intramolecular hydrogen bond between
The synthesis of an oligomeric urea containing Mo-Mo bonds along the backbone is reported. Reaction of the organometallic "diamine" [(7?5-C5H4CH2CH2NH3+)2Mo2(CO)6][N03-]2 with OCN(CH2)6NCO (hexamethylene diisocyanate, HMDI) in an interfacial synthesis gave [-NHCH2CH2C5H4(CO)3Mo-Mo-
The hotochemiatry of the [ -o C H 2 C ( O ) C~4 ( C O )~M o -M o ( C O ) 3 C~C ( O ) C H~~~O~~~C H~~C~O~-] n and [-OCH2CH2C6H4(CO)2Fe-Fe(C0)2C6H4CH2CH2OC(O)NH(CH2)6NHC(O)-]n (4) oligomers was investigated. Because of the metal-metal bonds along the oligomer backbone, these polyurethanes are photochemically reactive, undergoing reactions similar to the C~, M O~( C O )~ and Cp2Fe2(CO)4 dimers. Irradiation leads to homolysis of the metal-metal bonds, as evidenced by formation of C1-(CO) MoC5H4-R-C5H4Mo(C0),C1 or Cl(C0)2FeC6H4-R-CsH4Fe(CO)2Cl (R = CH2CH20C(0)NH(CH2)6N-HC(6)OCH2CH2 or C(0)CH20C(O)NH(CH2)6NHC(O)OCH2C(O)) when the oligomers are irradiated in the presence of CCL. In the presence of triethyl phosphite, disproportionation of the Mo-Mo and Fe-Fe bonded units occurred to give a fragmentation product containing (C5H4R)Mo(C0)c and (C6H4R)Mo-(CO)2(P(OEt)3)2+ or (C6H4R)Fe(C0)f and (C5H4R)Fe(CO)(P(OEt)&+ groups, respectively.Photochemical decomposition of the polyurethanes also occurred over several weeks to months in the solid state. Both light and oxygen are necessary for this decomposition in the solid state. It is proposed that cleavage of the metal-metal bonds leads to oligomer fragmentation and the formation of metal oxide species in these solid state reactions. Oligomer 2, containing the singly bonded C~(CO),M~-MO(CO)~C~ unit, was converted (photochemically or thermally) to a polymer containing triply bonded Cp(CO)2M~Mo(CO)2Cp groups.
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