The reaction of manganese carbonyl with tert-butylisocyanide: Synthesis and characterization of cis- and trans-[MnI(tBuNC)4(CN)(CO)]

Halbauer, Kathi; Görls, Helmar; Fidler, Tamara; Imhof, Wolfgang

doi:10.1016/j.jorganchem.2006.12.043

Cited by 18 publications

(4 citation statements)

References 62 publications

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“…Finally, the question of why the carbonyl ligands of compounds 2 are readily and completely replaced during reactions with CN p -FAr DarF2 and a mer -{Tc I (CN p -FAr DarF2 ) 3 } + core is formed, while no such reactions were observed for CN n Bu, CN t Bu, or CNCy remains. The fact that isocyanides should not be regarded as simple “CNR surrogates” of carbonyl ligands has been well accepted for a long time, and several examples of carbonyl/isocyanide exchange reactions have been reported. ,− In the chemistry of the group 7 elements, however, such replacements are mainly restricted to labilized carbonyl ligands. − ,,− The coordination properties of isocyanides are obviously governed by a complex interplay of their molecular orbitals. This results in substitution-specific and difficult-to-predict σ-donor and π-acceptor properties for the individual ligands, which may interfere additionally with restrictions given by the steric bulk of the residues .…”

Section: Resultsmentioning

confidence: 99%

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

et al. 2022

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Reactions of the alkyl isocyanide fac-[Tc(CO)3(CNR)2Cl] complexes (2) (CNR = CN n Bu or CN t Bu) with the sterically encumbered isocyanide CNp-FArDarF2 [DArF = 3,5-(CF3)2C6H3] allow a selective exchange of the carbonyl ligands of 2 and the isolation of the mixed-isocyanide complexes mer,trans-[Tc(CNp-FArDarF2)3(CNR)2Cl] (3). Depending on the steric requirements of the residues R, the remaining chlorido ligand can be replaced by another isocyanide ligand. Cationic complexes such as mer-[Tc(CNp-FArDarF2)3(CN n Bu)3]+ (4a) or mer,trans-[Tc(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)]+ (6) have been prepared in this way and isolated as their PF6 – salts. mer,trans-[Tc(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)](PF6) represents to the best of our knowledge the first transition-metal complex with three different isocyanides in its coordination sphere. Since the degree of the ligand exchange seems to be controlled both by the electronic and steric measures of the incoming isocyanides, we undertook similar reactions with the sterically less demanding p-fluorophenyl isocyanide, CNPhpF, which indeed readily led to the hexakis(isocyanide)technetium(I) cation through an exchange of all ligands in the staring materials [Tc2(CO)6(μ-Cl)3]− or fac-[Tc(CO)3(CNR)2Cl]. The influence of the substituents at the isocyanide ligands in such reactions has been reasoned with the density functional theory-derived electrostatic potential at the accessible surface of the corresponding isocyanide carbon atoms.

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Section: Resultsmentioning

confidence: 99%

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

et al. 2022

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“…In the past decade, metal-mediated cyanation involving isocyanides was reported for group 3 (Ln and U , ), group 6 (Mo, , W , ), group 7 (Mn), group 8 (Fe, , Ru), group 9 (Rh), and group 10 (Ni, Pd, , and Pt) species, and these examples will be considered accordingly below in this section.…”

Section: Cleavage Of the Cn–r Single Bond At Metal Centersmentioning

confidence: 99%

“…The reaction of Mn 2 (CO) 10 with CNBu t in the presence of CO (10 bar) leads to the isomeric mixture cis / trans -[Mn(CN)(CNBu t ) 4 (CO)] (toluene, 140 °C, sealed tube, overnight, yield not given), along with [Mn(CNBu t ) 6 ](CN) as a minor product . The fate of the tert -butyl group after the cyanation was not verified.…”

Section: Cleavage Of the Cn–r Single Bond At Metal Centersmentioning

confidence: 99%

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

et al. 2015

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“…For related literature, see: Braga et al (1993); Farrugia & Evans (2005); Hahn et al (2004); Ladell et al (1952); Bigorgne (1963a,b); Dö nnecke & Imhof (2003); Desiraju & Steiner (1999); Halbauer et al (2006Halbauer et al ( , 2007; ; ; Ostuka et al (1969Ostuka et al ( , 1971.…”

Section: Related Literaturementioning

confidence: 99%

Tris(tert-butyl isocyanide-κC)carbonylnickel(0)

2008

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The title compound, [Ni(C5H9N)3(CO)], was prepared from Ni(CO)4 and a tenfold excess of tert-butyl isocyanide. It crystallizes with two symmetry-independent molecules per asymmetric unit. The central Ni atom of each independent molecule has a nearly perfect tetrahedral coordination environment, comprising one carbon monoxide and three isocyanide ligands. The title compound is the first structurally characterized Ni0 compound with a mixed CO/RNC coordination.

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The reaction of manganese carbonyl with tert-butylisocyanide: Synthesis and characterization of cis- and trans-[MnI(tBuNC)4(CN)(CO)]

Cited by 18 publications

References 62 publications

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

Metal-Mediated and Metal-Catalyzed Reactions of Isocyanides

Tris(tert-butyl isocyanide-κC)carbonylnickel(0)

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