The first transition-metal isonitrilate: synthesis and characterization of cobalt complex K[Co(2,6-Me2C6H3NC)4]

Warnock, Garry F.; Cooper, N. John

doi:10.1021/om00109a043

Cited by 42 publications

(27 citation statements)

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“…[41] Interestingly, 6 represents the first isolable tin adduct of ah omoleptic isocyanide of aG roup 5m etal, M(CNR) 6 ,M = V, Nb,T a. Warnock and Cooper prepared Ph 3 SnCo(CNXyl) 4 in 1989 as ak ey derivative in their characterization of the first homoleptic isocyanidemetalate, [Co(CNXyl) 4 ] À . [42] Because the homoleptic cobalt isocyanides,C o 2 (CNR) 8 , R = tBu [43] and Xyl, [16] were reported to react with carbon monoxide (R = tBu, rapidly at 20 8 8Cu nder 1atm;R= Xyl, slowly at 40 8 8Cu nder 30 atm) to afford the respective salts [Co(CNR) 5 ][Co(CO) 4 ], the reaction of 5 with CO was examined. Treatment of deep red-violet solutions of 5 with CO (1 atm) at À65 8 8Cw ithin seconds gave ad ark green solution (of unknown nature).…”

Section: Methodsmentioning

confidence: 99%

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

et al. 2017

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Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO) and represents the only well-defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Two prior examples of homoleptic Ta complexes are known, Ta(benzene) and Ta(dmpe) , dmpe=1,2-bis(dimethylphosphano)ethane, but these have only been accessed via ligand co-condensation with tantalum vapor in a sophisticated metal-atom reactor. Consistent with its 17-electron nature, Ta(CNDipp) undergoes facile one-electron oxidation, reduction, or disproportionation reactions. In this sense, it qualitatively resembles V(CO) , the only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.

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Section: Methodsmentioning

confidence: 99%

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

et al. 2017

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“…Interestingly, 6 represents the first isolable tin adduct of a homoleptic isocyanide of a Group 5 metal, M(CNR) 6 , M=V, Nb, Ta. Warnock and Cooper prepared Ph 3 SnCo(CNXyl) 4 in 1989 as a key derivative in their characterization of the first homoleptic isocyanidemetalate, [Co(CNXyl) 4 ] − …”

Section: Figurementioning

confidence: 99%

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

et al. 2017

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Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO) 6 and represents the only well-defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Tw op rior examples of homoleptic Ta 0 complexes are known, Ta(benzene) 2 and Ta(dmpe) 3 ,d mpe = 1,2-bis(dimethylphosphano)ethane,but these have only been accessed via ligand cocondensation with tantalum vapor in as ophisticated metalatom reactor.C onsistent with its 17-electron nature,T a-(CNDipp) 6 undergoes facile one-electron oxidation, reduction, or disproportionation reactions.I nt his sense,i tq ualitatively resembles V(CO) 6 ,t he only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.Incontrast to vanadium and niobium, [1] isolable homoleptic complexes of zerovalent tantalum are quite rare,w ith only two examples presently known:T a(benzene) 2[2] and Ta-(dmpe) 3 , [3] dmpe = 1,2-bis(dimethylphosphano)ethane.A lso, these species are very poorly accessible because they are only available via tantalum vapor synthesis methods,which require specialized metal-atom reactors. [4] Although Ta(bipy) 3 ,bipy = a,a'-bipyridine, [5] and Ta(iPr 2 -dad) 3 , iPr 2 -dad = 1,4-diisopropyl-1,4-diazabuta-1,3-diene, [6] were originally suggested to be zerovalent tantalum complexes,later experimental and computational studies indicate that both compounds contain high-valent Ta V . [7] Perhaps the most interesting comparisons of homoleptic zerovalent complexes of Group 5m etals are for the 17electron hexacarbonyls of these species:V (CO) 6 is wellknown as the only paramagnetic unsubstituted metal carbonyl isolable under ambient conditions, [8] while Ta(CO) 6 [9] and Nb(CO) 6[10] have only been obtained at low temperatures as matrix isolated species and may be unstable above 50 K. Barybinss ynthesis of the 17-electron complex V(CNXyl) 6 , Xyl = 2,6-dimethylphenyl, which was far more thermally stable (m.p.1 59-160 8 8Cd ecomp.) [1i] than V(CO) 6 (decomp. 60-70 8 8C), [8] suggested that Ta(CNXyl) 6 and the niobium analog might be isolable.H owever,d espite success in the synthesis and isolation of [Ta(CNXyl) 7 ] + ,[Ta(CNXyl) 6 ] À ,and related complexes, [11, 12] attempts to isolate the corresponding elusive neutral homoleptic tantalum and niobium complexes uniformly failed. [13] Many years ago Mann, Gray,a nd Hammond reported on the zerovalent complex W(CNDipp) 6 , Dipp = 2,6-diisopropylphenyl, [14] and it was of interest to determine whether this more sterically encumbered isocyanide could stabilize the corresponding neutral tantalum complex. Initial results were promising and provided astructural characterization of the unique ditantalum salt [Ta-(CNDipp) 7 ][Ta(CNDipp) 6 ], [15] atype of compound previously unknown for homoleptic metal carbonyls and isocyanides, [16] and of significance as aformal disproportionation product of the desired Ta(CNDipp) 6 complex. Unfortunately,t his salt could not be obtained as ap ure bulk solid and the neutral species was not isolated, so ...

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“…P4 and CO2) and as catalysts for hydrogenation and hydroboration reactions. [23] Taking advantage of the well-known ability of isonitriles to stabilize low oxidation state transition metal complexes, [15], [16], [24] in combination with imposing rigidity, we were interested in exploring the potential of the above-mentioned chelating isonitrile ligands in the stabilization of highly-reduced iron complexes. We particularly questioned if polynuclear iron complexes with chelating bis(isonitrile) ligands can still be formed, for which to the best of our knowledge, no previous examples have been described in the literature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

Till¹,

Kelly²,

Ziegler³

et al. 2021

Preprint

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Divalent iron complexes trans-[FeBr2(BINC)2], [Cp*FeCl(BINC)] (Cp* = Me5C5) and [FeBr2(CNAr3NC)2] with chelat-ing bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr3NC (2,2’’-diisocyano-3,5,3’’,5’’tetramethyl-1,1’:3’,1’’-terphenyl) have been prepared and characterized. Their subsequent reduction yields di- and trinuclear compounds [Fe3(BINC)6], [Cp*Fe(BINC)]2, [Fe(CNAr3NC)2]2 and [K(Et2O)]2[Fe(CNAr3NC)2]2. The molecular structures of all new species were determined by X-ray crystallography. The molecular structures are compared to related iron carbonyl complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV-Vis-NIR spectroelectrochemistry. <br>

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The first transition-metal isonitrilate: synthesis and characterization of cobalt complex K[Co(2,6-Me2C6H3NC)4]

Cited by 42 publications

References 0 publications

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

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The first transition-metal isonitrilate: synthesis and characterization of cobalt complex K[Co(2,6-Me2C6H3NC)4]

Cited by 42 publications

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Ta(CNDipp)6: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)6: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)6: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

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Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Ta(CNDipp)₆: An Isocyanide Analogue of Hexacarbonyltantalum(0)