Syntheses of highly unsaturated isocyanides via organometallic pathwaysCCDC reference numbers 179717179718 and 836248836250. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt11382h

The carbon carbon coupling reaction by nucleophilic attack of (CO) 5 Cr(CNCF&z.dbd;CF 2 ) 1 by lithium or Grignard compounds 2ai yields the isocyanide complexes (CO) 5 Cr(CNCF&z.dbd;CFR) 3ai ( a R = CH&z.dbd;CH 2 , b R = CH&z.dbd;CF 2 , c R = C&z.tbd;CH, d R = C&z.tbd;CSiMe 3 , e R = C&z.tbd;CPh, f R = C&z.tbd;CC 6 F 4 OMe, g R = C&z.tbd;CC 6 H 3 (CF 3 ) 2 , h R = C 6 F 5 , i R = C 6 H 3 (CF 3 ) 2 ) as mixtures of E and Z isomers. The dinuclear complexes 5ac are obtained from the reaction of 1 with the dilithio or dimagnesium compound 4ac as the Z , Z -, E , Z - and E , E -isomers, respectively. (CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 7 is obtained as a mixture of Z , Z -, Z , E - and E , E -isomers from (CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CH 3d by Eglington-Glaser coupling. (CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 6 and (CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 7 react with octacarbonyldicobalt forming the cluster compounds Z , Z -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }Co 2 (CO) 6 ] Z , Z - 8 , E , Z -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }Co 2 (CO) 6 ] E , Z - 8 and E , E -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }Co 2 (CO) 6 ] E , E - 8 and Z , Z -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }{Co 2 (CO) 6 } 2 ] Z , Z - 9 , E , Z -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }{Co 2 (CO) 6 } 2 ] E , Z - 9 and E , E -[{ 2 - 2 -(CO) 5 Cr(CNCF&z.dbd;CFC&z.tbd;CC&z.tbd;CCF&z.dbd;CFNC)Cr(CO) 5 }{Co 2 (CO) 6 } 2 ] Z , Z - 9 , respectively. The crystal and molecular structures of E - 3d , Z - 3h , Z , Z - 8 , E , Z - 8 and Z , Z - 9 were elucidated by single-crystal X-ray crystallography. The carbon carbon coupling reaction by nucleophilic attack of the trifluoroethenyl isocyanide complex (CO) 5 Cr(CNCF&z.dbd;CF 2 ) by lithium or Grignard compounds yields isocyanide complexes as mixtures of E and Z isomers.