Synthesis of transition metal isocyanide compounds from carbonyl complexes via reaction with Li[Me3SiNR]

Abstract

The reaction between a transition metal carbonyl compound, L(n)MCO, and Li[Me(3)SiNR] yields the corresponding isocyanide derivative, L(n)MCNR, thereby providing a new route to transition metal isocyanide compounds that does not require the use of free isocyanides as reagents.

Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator

“…The t BuNC ligand is coordinated to iron at d Fe1‐C1 =1.874(4) Å. This lies between reported Fe‐(CN‐R) bond lengths of divalent [Fe II Cp(CO) 2 (CN‐Me)][BF 4 ] ( d Fe‐C =1.900(9) Å) and zero‐valent Fe(CO) n (CN‐ t Bu) m ( d Fe‐C =1.89 { n =4, m =1} 1.865(2) { n =3, m =2} 1.813(7) to 1.837(7) { n =0, m =5} Å) and is by 0.09 Å longer than in the related [Fe(CO)Cp* 2 ][AsF 6 ] 2 (cf. d Fe‐C =1.785(9) Å) .…”

Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator

“…The t BuNC ligand is coordinated to iron at d Fe1-C1 = 1.874 (4) . This lies between reported Fe-(CN-R) bond lengths of divalent [Fe II Cp(CO) 2 -(CN-Me)][BF 4 ] (d Fe-C = 1.900(9) [23] ) and zero-valent Fe-(CO) n (CN-t Bu) m (d Fe-C = 1.89 {n = 4, m = 1} [24] 1.865(2) {n = 3, m = 2} [25] 1.813 (7) to 1.837(7) {n = 0, m = 5} [26] ) and is by 0.09 longer than in the related [Fe(CO)Cp* 2 ][AsF 6 ] 2 (cf. d Fe-C = 1.785 (9) ).…”

Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered

“…One of the ethyl ester groups in the X-ray structure of 8 exhibits a minor positional disorder over two occupancies ( Figure 5 c and Figure S6 ). The pertinent metric data for the above new [(OC) 5 Cr(CNR)] species, along with those for [(OC) 5 Cr(CN t Bu)] [ 32 ], [(OC) 5 Cr(CNC 2 F 3 )] [ 10 ], and [(OC) 5 Cr(CN p -FAr DArF2 )] [ 6 ], are collated in Table 2 . For 6 , 7 , 8 , and 10 , the Cr–CNR bond length, which reflects the π-acceptor/σ-donor ability of the CNR ligand (particularly, the extent of π back-bonding interaction between the chromium(0) center and the isocyanide) [ 33 ], is significantly shorter than that in [(OC) 5 Cr(CN t Bu)].…”