X-ray photoelectron spectra of inorganic molecules. 31. Satellite structure associated with the core-electron binding energies of alkyl and aryl isocyanide complexes of the transition metals

Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4–/3–: Preparation of Homoleptic, Eight-Coordinate Methyl Isocyanide Complexes [W(CNMe)8]4+/5+

“…For the latter complex, the corresponding tungsten compound was only briefly mentioned in the literature. 13 For molybdenum, the crystal structures of [Mo(CNR) 7 ][PF 6 ] 2 are also known (R = cyclohexyl, phenyl). 11,14 Interestingly, the seven-coordinate chromium complex [Cr(CN t Bu) 7 ][PF 6 ] 2 also exists.…”

“…Raman (1064 nm, in cm −1 ): ν̃2957 s, 2282 s. 1 H NMR (700 MHz, CD 3 CN, 25 °C): δ 3.85 (s, CH 3 ). 13 C NMR (176 MHz, CD 3 CN, 25 °C): δ 31.82 (CNMe), 115.30 (CNMe). 15 N HMQC (71 MHz, CD 3 CN, 25 °C): δ 140 (CNMe).…”

“…IR (ATR, in cm −1 ): ν̃2964 w, 2276 m, 1436 w, 1407 w, 893 m, 693 s, 481 w, 465 w. Raman (1064 nm, in cm −1 ): ν̃2968 s, 2305 s, 2289 s, 1404 m, 681 m. 1 H NMR (700 MHz, CD 3 CN, 25 °C): δ 3.85. 13 C NMR (176 MHz, CD 3 CN, 25 °C): δ 31.82, 115.30. 19 F NMR (377 MHz, CD 3 CN, 25 °C): δ −66.06 (q, 1 J 75 As− 19 F = 932 Hz).…”

“…The existence of at least two species in the mixture was also confirmed via DOSY NMR, although the structure of the side product could not be assigned with certainty. 13 C chemical shifts were obtained by two-dimensional NMR spectroscopy (HMQC, HMBC). 13 C signals for the isocyanide carbon were in the range of 115.3 ppm (major component) and 112.5 ppm (minor component), while only one signal for the methyl group could be observed (δ 31.8 ppm).…”

Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4−/3−: Preparation of Homoleptic, Eight-coordinate Methylisocyanide Complexes [W(CNMe)8]4+/5+

“…For the latter, the corresponding tungsten compound is only briefly mentioned in the literature. 10 For molybdenum, also the crystal structures of [Mo(CNR)7][PF6]2 are known (R= cyclohexyl, phenyl). 8,11 Interestingly, also a seven-coordinate chromium complex [Cr(CN t Bu)7][PF6]2 exists.…”