Alkyl and alkaneimidoyl derivatives of Nickel(II) That contain the bulky CH(SiMe3)2 Group

Indenylmethyl-molybdenum and -tungsten compounds containing isocyanide ligands. Formation and study of isomeric η2-iminoacyls and η3-1-azaallyls

“…This is now recognized as a quite general phenomenon 12 that has been observed even in nickel() η 2 -iminoacyls. 13 A slip distortion of the co-ordinated indenyl ligand, similar to that previously discussed for 2, is also apparent in this compound. Thus the bonds from W to C(1), C(4) and C(5) average 2.33 Å, while those to C(2) and C(3) are 0.13 Å longer (2.46 Å, average).…”

“…1 H NMR (C 6 D 6 ): δ Ϫ0.20 (s, 3 H, MoMe cis ), 0.21 (s, 3 H, MoMe trans ), 0.79 (s, 9 H, CMe 3 cis ), 0.97 (s, 9 H, CMe 3 trans ), 4.91 (overlapping triplets, H y , both isomers, 3 J = 2.9 Hz), 5.24, 5.38 (overlapping multiplets, H x and H z of both isomers) and 6.70-7.10 (overlapping multiplets, H e-h , both isomers). 13 [W( 5 -C 9 H 7 )Me(CO) 2 (CNBu t )] 2. This complex was prepared by a method analogous to that described above for 1.…”

“…Extraction into light petroleum, followed by concentration and crystallization at Ϫ30 ЊC, resulted in the deposition of dark red needles of 3. = 8.4, H h ) and 6.89 (d, 1 H, 3 J = 8.4 Hz, H e ) 13. C-{ 1 H} NMR (CD 3 COCD 3 ): δ 18.6 (MeC᎐ ᎐ N), 29.8 (CMe 3 ), 57.6 (CMe 3 ), 80.7 (C z ), 81.6 (C x ), 93.9 (C y ), 115.6, 119.0 (C d and C i ), 123.9, 124.4, 124.9, 125.3 (C e-h ), 188.5 (MeC᎐ ᎐ N), 249.5, 252.5 (CO).…”

“…13 C-{ 1 H} NMR (CD 3 COCD 3 ): δ 31.6 (CMe 3 ), 39.5 (CH 2 , 1 J CH = 158), 58.0 (CMe 3 ), 73.7 (C z ), 76.5 (C x ), 89.4 (C y ), 117.0 (CH c , 1 J CH = 166 Hz), 118.8, 121.9 (C d and C i ), 125.6, 126.5, 127.0, 127.6 (C e-h ), 237.3, 237.4 (CO).…”

“…CO ) 1. H NMR (C 6 D 6 ): δ Ϫ0.09 (s, 3 H, WMe cis ), 0.33 (s, 3 H, WMe trans ), 0.83 (s, 9 H, CMe 3 cis ), 1.03 (s, 9 H, CMe 3 trans ), 4.88 (overlapping triplets, H y , both isomers, 3 J = 2.8), 5.22 (d, Hx /H z , trans isomer, 3 J = 2.9 Hz), 5.31, 5.35 (br m, H x /H z , cis isomer) and 6.60-7.00 (overlapping multiplets, H e-h , both isomers) 13. C-{ 1 H} NMR (C 6 D 6 ): δ Ϫ24.1 (WMe trans ), Ϫ20.4 (WMe cis ), 29.8 (CMe 3 trans ), 30.6 (CMe 3 cis ), 56.5 (CMe 3 cis ), 75.9, 77.3 (C x and C z , cis isomer), 78.3 (C x and C z , trans isomer), 87.5 (C y , cis isomer) 88.7 (C y , trans isomer), 109.4, 113.3 (C d and C i , cis isomer), 124.0-126.0 (overlapping signals, C e-h , both isomers), 221.6 (2 CO), 229.6, 240.8 (CO).…”