17595-21-0Relevant academic research and scientific papers
Specific formation of isocyanide iron complexes by reaction of primary carbamoyl ferrates with oxalylchloride
Luart, Denis,Salaün, Jean-Yves,Patinec, Véronique,Rumin, René,Des Abbayes, Hervé
, p. 656 - 660 (2008/10/08)
Reaction of primary carbamoyl ferrates {(CO)4Fe[C(O)NHR]} - (R=Me, Et, allyl, decyl, cyclohexyl, t-butyl, benzyl, phenyl) with 1/2 equiv. of oxalylchloride affords cis-bis-carbamoyl intermediates: (CO) 4Fe[C(O)NHR]2 which thermally give rise, in good yields, to the mono-isocyanide complexes (CO)4Fe(CNR). The mechanism of the reaction is discussed. Via a similar process, an alkoxycarbamoyl intermediate (CO)4Fe[C(O)NHR](CO2Me) affords Fe(CO)5 and 1,3-dialkylurea.
Reactions of dianionic carbonylmetalates with heteroallenes: Reduction of carbonyl sulfide, isothiocyanates, isocyanates, and carbodiimides by group 6 and 8 carbonylmetalates
Lee, Gary R.,Cooper, N. John
, p. 1538 - 1544 (2008/10/08)
Dianionic carbonylmetalates of the group 6 and group 8 metals can reduce a number of heteroallenes X=C=Y to coordinated O≡X ligands, provided X is a first-row element (N or O) which can form a strong triple bond with C. Thus Na2[M(CO)4] (M = Fe, Ru) and Na2[M(CO)5] (M = Cr, W) react readily with COS to give [M(CO)5] (M = Fe, Ru) and [M(CO)6] (M = Cr, W) in good yield, as established by absorbance mode IR for Fe and W and by isolation of the known derivatives [M(CO)4I2] (M = Fe, Ru) and [N(n-Bu)4][M(CO)5Br] (M = Cr, W), while CS2 does not give thiocarbonyl complexes with Na2[W(CO)5] or Na2[Fe(CO)4]. It is suggested on the basis of IR and stoichiometry that the COS reductions are reductive disproportionations leading to thiocarbonate formation. Isothiocyanates RNCS (R = Ph, Me) give moderate yields of the corresponding isonitrile complexes [M(CO)4(CNR)] with Na2[Fe(CO)4], but not with Na2[Ru(CO)4]. A similar reaction of PhNCS with Na2[Cr(CO)5] gives low yields of [Cr(CO)5(CNPh)], but [W(CO)5(CNPh)] can only be isolated after addition of oxalyl chloride to the intermediate isothiocyanate complex. Reduction of PhNCO with Na2[W(CO)5] leads to 84% and 5% solution yields of [W(CO)6] and [W(CO)5(CNPh)], respectively, consistent with control of the reduction of unsymmetrical heteroallenes by the relative triple bond strengths in the product C≡X ligands (C≡O > C≡N > C≡S).
Catalysed and Non-catalysed Reaction Between and Isonitriles
Albers, Michel O.,Coville, Neil J.,Singleton, Eric
, p. 1069 - 1080 (2007/10/02)
The reaction between and isonitrile, RNC, is catalysed by CoCl2*H2O and readily yields the complexes (n = 1-3, R = Me, C6H11, tBu, PhCH2, Ph, 2,6-Me2C6H3, or 2,4,6-Me3C6H2; n = 4, R = tBu; n = 4 or 5, R = Ph, 2,6-Me2C6H3, or 2,4,6-Me3C6H2).The high-yield synthesis of from and RNC in the absence of catalyst is also reported.Trimethylamine N-oxide has been used to synthesize from and RCN and results are compared with the CoCl2 catalysed reaction.All products were characterized by i.r. and n.m.r. spectroscopy.The higher substituted derivatives were further characterized by reaction with I2 and tetracyanoethylene (tcne) and gave (n = 2, R = tBu, PhCH2, or 2,6-Me2C6H3; n = 3, R = tBu or 2,6-Me2C6H3; n = 4, R = 2,6-Me2C6H3) and cis- and trans- from appropriate starting materials.Mechanistic data suggest that the reaction occurs via attack of catalyst at a co-ordinated CO ligand.Subsequent attack by unco-ordinated RNC in an intermolecular, non-bridging mechanism leads to the required isonitrile derivatives.
