Experimental and ab initio MO studies on the IR spectra and structure of pyridinium dicyanomethylide and trimethylammonium dicyanomethylide

Scaling of Computed Cyano-Stretching Frequencies and IR Intensities of Nitriles, Their Anions, and Radicals

“…Objects studied, No . (new individual numbering), species, reference, 1 , HOOCCH 2 CN; 2 , NCCH 2 COOCH 3 ; 22 3, NCCH 2 CONH 2 ; 77 4 , 3-amino-2-butenenitrile; 5a , NCCH 2 CN [our data]; 5b , NCCH 2 C 15 N [our data]; 6 , benzonitrile; 7 , 4-methylbenzonitrile; 8 , 3-methylbenzonitrile; 9 , 4-F 3 CC 6 H 4 CN; 10 , 4-C 2 H 5 OOCCH 2 C 6 H 4 CN; 11, 4-NCC 6 H 4 CN; 12, 3-NCC 6 H 4 CN; 13 , 4-HOOCC 6 H 4 CN; 14 , 3-HOOCC 6 H 4 CN; 15 , 4-cyanoacetanilide; 16 , 4-CH 3 OC 6 H 4 CN; 17 , 3-CH 3 OC 6 H 4 CN; 18 , 4-HOC 6 H 4 CN; 19, 3-HOC 6 H 4 CN; 20 , 4-HOC 6 H 4 CN; 21 , 4-cyanobenzamide [our data]; 22 , 4-O 2 NC 6 H 4 CN; 23 , 4-H 2 NC 6 H 4 CN; 24 , 4-(CH 3 ) 2 NC 6 H 4 CN; 25 , C 6 H 5 CH 2 CN; 26 , 4-O 2 NC 6 H 4 CH 2 CN; 27 , 4-NCC 6 H 4 CH 2 NO 2 ; 28, 4-NCC 6 H 4 CH 2 CN; 29 , 3-NCC 6 H 4 CH 2 CN; 30 , 2-NCC 6 H 4 CH 2 CN; 31 , benzilidenemalononitrile; 32 , 4-hydroxybenzilidenemalononitrile; 33 , phenylmalononitrile; 34 , pyridinium dicyanomethylide; anions of: 35 , NCCH 2 COOH; 36 , NCCH 2 COOCH 3 ; 37 , NCCH 2 CONH 2 ; dianion of 38 , NCCHCONH 2 ; anions of 39 , 3-amino-2-butenenitrile; 40a , NCCH 2 CN [our data]; 40b , NCCH 2 C 15 N [our data]; 41a , (NC) 3 CH; 41b , (NC) 2 CHC 15 N; 42 , 4-HOC 6 H 4 CN; 43 , 3-HOC 6 H 4 CN; 44 , 2-HOC 6 H 4 CN; 45 , 4-cyanobenzamide [our data]; 46 , 4-HOOCC 6 H 4 CN; 47 , 3-HOOCC 6 H 4 CN; 48 , 4-cyanoacetanilide; 49 , 3-cyanoacetanilide; 50 , 4-HOOCCH 2 C 6 H 4 CN; dianion of 51 , 4-HOOCCHC 6 H 4 CN; anions of 52 , 4-NCC 6 H 4 CH 2 CN; 53 , 3-NCC 6 H 4 CH 2 CN; 54 , 2-NCC 6 H 4 CH 2 CN; 55 , 4-hydroxybenzilidenemalononitrile; 56 , phenylmalononitrile …”

“…To find statistically reliable correlations between 68 cyano-stretching frequencies of 45 nitrile molecules within 11 basis sets of the B3LYP theory (Supporting Information, Table S1) ( No. , species studied; experimental data from) 1a , HCN; 1b , DCN; 1c , HC 15 N; 1d , H 13 CN; 2a , CH 3 CN; 2b , CD 3 CN; 2c , CH 3 C 15 N; 2d , CH 3 13 CN; 2e , 13 CH 3 CN; 2f , CD 3 13 CN; 3 , CH 3 CH 2 CN; 4 , (CH 3 ) 2 CHCN; 5 , cyclopropanecarbonitrile; 6 , cyclobutanecarbonitrile; 7 , cyclopentanecarbonitrile; 8 , cyclohexanecarbonitrile; 9a , NCCH 2 CN [our data]; 9b , NCCH 2 C 15 N [our data]; 10 , NCCH 2 CH 2 CN; 44 11 , CH 2 CHCN; 12 , trans- NCCHCHCN; 13 , cis- NCCHCHCN; 14 , (NC) 2 CC(CN) 2 ; 15 , HCCCN; 16 , C 6 H 5 CN; 17 , 4-HOC 6 H 4 C;N 18 , 4-H 2 NC 6 H 4 CN; 19 , 4-(CH 3 ) 2 NC 6 H 4 CN; 20 , 4-cyanobenzamide [our data]; 21a , 4-O 2 NC 6 H 4 CN; 21b , 4-O 2 NC 6 H 4 C 15 N; 22a , 4-NCC 6 H 4 CN; 22b , NCC 6 H 4 C 15 N; 23 , 4-F 3 CC 6 H 4 CN; 24 , 3-amino-2-butenenitrile; 25 , 1,1-dicyano-2-diethylaminoethene; 26, 1,1-dicyano-2,2-bis(diethylamino)ethane; 27, pyridinium dicyanomethylide; 28, trimethylamonium dicyanomethylide; 29 , diazonium dicyanomethylide; 30 , HOOCCH 2 CN; 31 , CH 3 OOCCH 2 CN; 32 , HOCN , 33 , HSCN , 34 , FCN; 35 , ClCN; 36 , BrCN; 37 , FCH 2 CN; 38 , ClCH 2 CN; , 39 , BrCH 2 CN; 40 , F 3 CCN; 41 , Cl 3 CCN; 42 , Br 3 CCN; 43 , FCCCN; 44 , ClCCCN; 45 , BrCCCN …”