Reactions of compounds containing nickel-nickel, nickel-molybdenum, and nickel-tungsten bonds with allene and 1,1-dimethylallene. X-ray diffraction studies of the .pi.-allylic complexes NiMo(.mu.-CO)(CO){.mu.-.eta.3,.eta.3-C9H12}(.eta.5-C5H5)(.eta.5-C5H4Me) and NiMo(.mu.-CO)(CO){.mu.-.eta.1,.eta.3-C(Me)C(Me)CH2}(.eta.5-C5H5)(.eta.5-C5H4Me) (Ni-Mo)
“…Reaction of allene with [(OC)Cp‘Mo(μ-CO) 2 NiCp(CO)] gives the tris-allyl-bridged species [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp] (see Figure ) in very low yield (see section V.H). The X-ray crystal structure shows that the two metals are far-removed from one another . Similar compounds bridged by iminoacyl ligands have been obtained from the reaction of isonitriles RNC (R = Me, t Bu) with [Cp 2 ClZr(μ-CHCH)RuCp(PMe 3 ) 2 ], giving [Cp 2 ClZr(μ-RNCCHCH- κ Zr N , κ Zr C , κ Ru C ‘)RuCp(PMe 3 ) 2 ] (see Figure ) …”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 64%
“… 41 Crystal structure of [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp]. Reprinted from ref . Copyright 1991 American Chemical Society. 42 Crystal structure of [Cp 2 ClZr(μ- t BuNCCMe=CH)RuCp(PMe 3 ) 2 ].…”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 99%
“…Crystal structure of [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp]. Reprinted from ref . Copyright 1991 American Chemical Society.…”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 99%
“…An X-ray crystal structure determination showed this to be [(OC) 2 Cp‘Mo{μ-(H 2 C) 2 CCH 2 C(CH 2 )C(CH 2 ) 2 }NiCp] (see Figure ), in which each metal center is η 3 -bound to an allyl moiety. The bridging ligand arises from the trimerization of allene …”
“…Reaction of allene with [(OC)Cp‘Mo(μ-CO) 2 NiCp(CO)] gives the tris-allyl-bridged species [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp] (see Figure ) in very low yield (see section V.H). The X-ray crystal structure shows that the two metals are far-removed from one another . Similar compounds bridged by iminoacyl ligands have been obtained from the reaction of isonitriles RNC (R = Me, t Bu) with [Cp 2 ClZr(μ-CHCH)RuCp(PMe 3 ) 2 ], giving [Cp 2 ClZr(μ-RNCCHCH- κ Zr N , κ Zr C , κ Ru C ‘)RuCp(PMe 3 ) 2 ] (see Figure ) …”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 64%
“… 41 Crystal structure of [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp]. Reprinted from ref . Copyright 1991 American Chemical Society. 42 Crystal structure of [Cp 2 ClZr(μ- t BuNCCMe=CH)RuCp(PMe 3 ) 2 ].…”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 99%
“…Crystal structure of [(OC) 2 Cp‘Mo{μ-C 3 H 4 CH 2 C(CH 2 )C 3 H 4 }NiCp]. Reprinted from ref . Copyright 1991 American Chemical Society.…”
Section: Compounds Bridged By An Alkyl Chainmentioning
confidence: 99%
“…An X-ray crystal structure determination showed this to be [(OC) 2 Cp‘Mo{μ-(H 2 C) 2 CCH 2 C(CH 2 )C(CH 2 ) 2 }NiCp] (see Figure ), in which each metal center is η 3 -bound to an allyl moiety. The bridging ligand arises from the trimerization of allene …”
“…In contrast to the iron carbonyl derivative, the manganese carbonyl derivative was the trans isomer, necessarily without a formal metal–metal bond. Subsequently the related carbonyl-free nickel complex trans -(η 3 ,η 3 -TME)Ni 2 Cp 2 (Cp = η 5 -C 5 H 5 ) was prepared in low yield from Cp 2 Ni 2 (μ-CO) 2 and allene and structurally characterized by X-ray crystallography. − In all three of these stable TME derivatives both metal atoms have the favored 18-electron configuration. − …”
The tetramethyleneethane (TME) ligand
is found in the η3,η3 complex trans-(η3,η3-TME)Ni2Cp2 and the η4,η4 complex trans-(η4,η4-TME)Co2Cp2, which have both been synthesized
and structurally characterized by X-ray crystallography. The structures
of the complete series of (TME)M2Cp2 derivatives
of the first-row transition metals from Ti to Ni have now been investigated
by density functional theory. The experimentally known nickel and
cobalt complexes are found to have closed-shell electronic ground
states. The lowest energy structure for the iron complex is the triplet
spin state trans-(η4,η4-TME)Fe2Cp2 structure with geometry
similar to that of the lowest energy cobalt structure. All of the
low-energy (TME)M2Cp2 structures for manganese
and the first-row transition metals to the left of manganese (Cr,
V, and Ti) exhibit cis-(η4,η4-TME)M2Cp2 stereochemistry, thereby
providing the possibility for direct metal–metal interactions.
Vanadium is the only first-row transition metal to the left of cobalt
where the lowest energy (TME)M2Cp2 structure
is a singlet spin state, suggesting limited applicability of the 18-electron
rule in these systems. The frontier molecular orbitals of these cis-(η4,η4-TME)M2Cp2 systems have been examined in order to provide insight
regarding metal–metal bonding. Thus, low-energy cis-(η4,η4-TME)Mn2Cp2 structures are found in both quintet and triplet spin states
with formal MnMn double bonds. The lowest energy cis-(η4,η4-TME)Cr2Cp2 and cis-(η4,η4-TME)Ti2Cp2 structures have triplet
spin states with a formal CrCr triple bond and a formal TiTi
double bond, respectively. The lowest energy cis-(η4,η4-TME)V2Cp2 structure
is a singlet structure with a formal VV triple bond.
Reactions of H2Os3(CO)10, 3, with the monophosphite‐substituted and non‐substituted tungsten propargyl and allenyl carbonyl complexes Cp(CO)2LWCH2C≡CH (1a, L = CO; 1b, L = P(OMe)3) and Cp(CO)2LWCH = C = CH2 (2a, L = CO; 2b, L = P(OMe)3) were investigated. In the reaction of 1b with 3, a tetranuclear complex 4b is obtained. The molecules of 4b crystallize as Cp(CO)2[P(OMe)3]W(μ, η1, η2‐CH2CH=CH)(μ‐H)Os3(CO)l0 in space group PI with a = 9.490 (4), b = 13.072 (7), c = 13.770 (9) Å, α = 91.89 (5), β = 106.71 (5), γ = 104.07(4)°, V = 1577(2) Å3, Z = 2. In the reaction of 2a with 3, from the reaction mixture exposed to air followed by workup using silica‐gel packed column chromatography, a complex consisting of two triosmium clusters bridged by a hexadiene ligand from the coupling of allenyl ligand was obtained. The molecules of the hexanuclear complex crystallize as [CH2CH = CH)2(μH)2OS6(CO)20in space group P21/c with a = 14.448 (7), b = 13.689 (4), c = 19.224 (4) Å, β = 107.14(3)°, V = 3633 (2) Å Z = 4.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
