Synthesis and reactions of dicarbonyl(.eta.-cyclopentadienyl)dihydridorhenium(III)

Abstract

the basis of steric requirements due to the larger coordination number and of the different oxidation number of the metal. ConclusionsThe triethylphosphine-carbon disulfide adduct Et3P-CS2 is a very versatile ligand. Indeed this zwitterion can act as a monodentate or bidentate donor by means of its electron-rich sulfur atoms, but it can be also bonded to Synthesis and Reactions of Dicarbonyl(77-cyclopentadienyl)dihydridorhenium(III)

The hydride route to the preparation of dinitrogen complexes

“…92 Synthesis of the rhenium derivative, CpRe(CO) 2 (N 2 ), is only possible via the latter synthetic pathway 93 due to the stability of CpRe(CO) 2 H 2 towards dinitrogen. 91,94 Once again, it is the third row hydrido complexes that are inert to substitution by N 2 . While a similar situation is noticeable for the group 8 and group 9 hydrido complexes (vide supra), this trend becomes less explicit for the group 6 metals.…”

Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene

“…Interestingly, the reactions also stoichiometrically produced biphenyl (entries 1 and 2 in Table 1). Further activation of the C-I bond and the relatively inert C-Cl bond with trans-2a was also conducted by photolysis of trans-2a with iodo-benzene and chlorobenzene in benzene, which similarly provided the corresponding mono(rhenium dihalides) (8,10) and di(rhenium dichlorides) (9), as well as the biphenyl (Scheme 2) (entries 3 and 4, Table 1). These results are consistent with our recent report on the chemical reactions of (η 5 -C 5 R 5 )Re(CO) 3 (R = Me, H) with aryl halides in benzene (entries 5 and 6, Table 1), 12 but different from that of Klahn's on the photolysis of Cp*Re(CO) 3 in neat aryl chlorides, or in saturated hexane solution of aryl chlorides, which mainly yielded the corresponding insertion products Cp*Re(CO) 2 (Ar)Cl.…”

“…The chemistry of cyclopentadienylrheniumtricarbonyl complexes (η 5 -C 5 R 5 )Re(CO) 3 (R = H, Cp or Me, Cp*) has been investigated widely in recent decades, especially serving as useful precursors to produce complexes of the type (η 5 -C 5 R 5 )Re(CO) 2 L when they are irradiated in the presence of PR 3 , 1 alkenes, 2 or THF. 3 Besides, (η 5 -C 5 R 5 )Re(CO) 3 could also be used in the catalytic borylation of alkanes, 4 activation of the C-H bond in alkanes 5 or cycloalkanes, 6 activation of the Si-H bond in silanes, 7 and the H-H bond in H 2 , 8 activation of the C-H, 9 C-F, 10 or C-Cl 11 bond in aryl halides and allyl halides. Recently, we studied the photochemical reactions of (η 5 -C 5 R 5 )-Re(CO) 3 with aryl halides in benzene, and observed the stoichiometric formation of biphenyl, as well as the corresponding rhenium dicarbonyl products (η 5 -C 5 R 5 )Re(CO) 2 X 2 (X = Cl, Br, or H).…”

Low-valent Organorhenium Compounds

“…Dihydride (35) is available f r o m photolysis of [Re(CO) 3 (Cp)] in supercritical xenon pressurized with H 2 , 119 and photolysis of [Re(CO) 3 (Cp)] and Et 2 SiH 2 in heptane leads to (35) in 49% yield. 120 A more convenient preparation of (35) is f r o m Zn/HOAc reduction o f a mixture of cis-and toms-[ReBr 2 (CO) 2 (Cp)]. 121 The monohydride [ReH(CO) 2 (Cp)]~ (36) is formed upon deprotonation of trans- (35) with KOH, but no reaction is observed upon attempted deprotonation o f monohydride (36) with LiNPr'^ in either glyme or MeCN.…”