10
1 Nitrile Imines and Their Properties
21. Delaittre G, Goldmann AS, Mueller JO, Barner-Kowollik C (2015) Efficient photochemical
approaches for spatially resolved surface functionalization. Angew Chemie Int Ed 54:11388–
11403
22. Huisgen R (1963) 1,3-Dipolar cycloadditions. past and future. Angew Chemie Int Ed English
2:565–598
23. Caramella P, Houk KN (1976) Geometries of nitrilium betaines. The clarification of apparently
anomalous reactions of 1,3-dipoles. J Am Chem Soc 98:6397–6399
24. Bock H, Dammel R, Fischer S, Wentrup C (1987) Nitrile imines RC = N(+) − N(−) −
Si(CH 3 ) 3 : optimization of gas phase synthesis and assignment of their photoelectron spectra.
Tetrahedron Lett 28:617–620
25. Wong MW, Wentrup C (1993) Structure of nitrilimine: allenic or propargylic? J Am Chem Soc
115:7743–7746
26. Bégué D, Qiao GG, Wentrup C (2012) Nitrile imines: matrix isolation, IR spectra, structures,
and rearrangement to carbodiimides. J Am Chem Soc 134:5339–5350
27. Caramella P, Gandour RW, Hall JA, Deville CG, Houk KN (1977) A derivation of the shapes
and energies of the molecular orbitals of 1,3-dipoles. Geometry optimizations of these species
by MINDO/2 and MINDO/3. J Am Chem Soc 99:385–392
28. Granier M, Baceiredo A, Huch V, Veith M, Bertrand G (1991) X-ray crystal structure and
reactivity of an N-Phosphonio-substituted nitrilimine: a stable electrophilic nitrilimine. Inorg
Chem 30:1161–1162
29. Hiberty PC, Leforestier C (1978) Expansion of molecular orbital wave functions into valence
bond wave functions. A simplified procedure. J Am Chem Soc 100:2012–2017
30. Moffat J (1979) The isomers of diazomethane. J Mol Struct 52:275–280
31. Thomson C, Glidewell C (1983) An ab initio study of the relative stabilities of the isomers of
CH 2 N 2 and SiH 2 N 2 . J Comput Chem 4:1–8
32. Kahn SD, Hehre WJ, Pople JA (1987) Hartree-fock descriptions of 1,3-dipoles. Zwitterions,
1,3-diradicals, or hypervalent species? J Am Chem Soc 109:1871–1873
33. Guimon C, Khayar S, Gracian F, Begtrup M, Pfister-Guillouzo G (1989) HeI photoelectron and
theoretical study of the gas phase flash pyrolysis of tetrazole and analysis of CN 2 H 2 energy
hypersurface. Chem Phys 138:157–171
34. Hiberty PC, Ohanessian G (1982) Comparison of minimal and extended basis sets in terms of
resonant formulas. application to 1,3 dipoles. J Am Chem Soc 104:66–70
35. Kawauchi S, Tachibana A, Mori M, Shibusa Y, Yamabe T (1994) Molecular structures and
relative stability of SiH 2 N 2 and CH 2 N 2 isomers. J Mol Struct 310:255–267
36. Maier G, Eckwert J, Bothur A, Reisenauer HP, Schmidt C (1996) Photochemical fragmentation
of unsubstituted Tetrazole, 1,2,3-triazole, and 1,2,4-triazole: first matrix-spectroscopic
identification of nitrilimine HCNNH. Liebigs Ann 1041–1053
37. Goldberg N, Fiedler A, Schwarz H (1994) Gas-phase generation and characterization of
nitrileimine, HCNNH: a new, stable isomer of diazomethane. Helv Chim Acta 77:2354–2362
38. Kiselev VG, Cheblakov PB, Gritsan NP (2011) Tautomerism and thermal decomposition of
tetrazole: high-level ab initio study. J Phys Chem A 115:1743–1753
39. Ríos-Gutiérrez M, Domingo LR (2019) The carbenoid-type reactivity of simplest nitrile imine
from a molecular electron density theory perspective. Tetrahedron 75:1961–1967
40. Granier M, Baceiredo A, Dartiguenave Y, Dartiguenave M, Menu MJ, Bertrand G (1990)
Synthesis and reactivity of stable phosphorus-substituted nitrilimines. X-ray crystal structure
of C-[bis (diisopropylamino) thioxophosphoranyl]-N-[bis (diisopropylamino) phosphanyl]
nitrilimine. J Am Chem Soc 112:6277–6285
41. Réau R, Veneziani G, Dahan F, Bertrand G (1992) A straightforward synthesis of nitrilimines;
X-ray crystal structure of a nitrilimine stabilized by non-heteroatom substituents. Angew
Chemie Int Ed English 31:439–440
42. Fauré J-L, Réau R, Wong MW, Koch R, Wentrup C, Bertrand G (1997) Nitrilimines:
evidence for the allenic structure in solution, experimental and ab initio studies of the
barrier to racemization, and first diastereoselective [3 + 2]-cycloaddition. J Am Chem Soc
119:2819–2824
1 Nitrile Imines and Their Properties
21. Delaittre G, Goldmann AS, Mueller JO, Barner-Kowollik C (2015) Efficient photochemical
approaches for spatially resolved surface functionalization. Angew Chemie Int Ed 54:11388–
11403
22. Huisgen R (1963) 1,3-Dipolar cycloadditions. past and future. Angew Chemie Int Ed English
2:565–598
23. Caramella P, Houk KN (1976) Geometries of nitrilium betaines. The clarification of apparently
anomalous reactions of 1,3-dipoles. J Am Chem Soc 98:6397–6399
24. Bock H, Dammel R, Fischer S, Wentrup C (1987) Nitrile imines RC = N(+) − N(−) −
Si(CH 3 ) 3 : optimization of gas phase synthesis and assignment of their photoelectron spectra.
Tetrahedron Lett 28:617–620
25. Wong MW, Wentrup C (1993) Structure of nitrilimine: allenic or propargylic? J Am Chem Soc
115:7743–7746
26. Bégué D, Qiao GG, Wentrup C (2012) Nitrile imines: matrix isolation, IR spectra, structures,
and rearrangement to carbodiimides. J Am Chem Soc 134:5339–5350
27. Caramella P, Gandour RW, Hall JA, Deville CG, Houk KN (1977) A derivation of the shapes
and energies of the molecular orbitals of 1,3-dipoles. Geometry optimizations of these species
by MINDO/2 and MINDO/3. J Am Chem Soc 99:385–392
28. Granier M, Baceiredo A, Huch V, Veith M, Bertrand G (1991) X-ray crystal structure and
reactivity of an N-Phosphonio-substituted nitrilimine: a stable electrophilic nitrilimine. Inorg
Chem 30:1161–1162
29. Hiberty PC, Leforestier C (1978) Expansion of molecular orbital wave functions into valence
bond wave functions. A simplified procedure. J Am Chem Soc 100:2012–2017
30. Moffat J (1979) The isomers of diazomethane. J Mol Struct 52:275–280
31. Thomson C, Glidewell C (1983) An ab initio study of the relative stabilities of the isomers of
CH 2 N 2 and SiH 2 N 2 . J Comput Chem 4:1–8
32. Kahn SD, Hehre WJ, Pople JA (1987) Hartree-fock descriptions of 1,3-dipoles. Zwitterions,
1,3-diradicals, or hypervalent species? J Am Chem Soc 109:1871–1873
33. Guimon C, Khayar S, Gracian F, Begtrup M, Pfister-Guillouzo G (1989) HeI photoelectron and
theoretical study of the gas phase flash pyrolysis of tetrazole and analysis of CN 2 H 2 energy
hypersurface. Chem Phys 138:157–171
34. Hiberty PC, Ohanessian G (1982) Comparison of minimal and extended basis sets in terms of
resonant formulas. application to 1,3 dipoles. J Am Chem Soc 104:66–70
35. Kawauchi S, Tachibana A, Mori M, Shibusa Y, Yamabe T (1994) Molecular structures and
relative stability of SiH 2 N 2 and CH 2 N 2 isomers. J Mol Struct 310:255–267
36. Maier G, Eckwert J, Bothur A, Reisenauer HP, Schmidt C (1996) Photochemical fragmentation
of unsubstituted Tetrazole, 1,2,3-triazole, and 1,2,4-triazole: first matrix-spectroscopic
identification of nitrilimine HCNNH. Liebigs Ann 1041–1053
37. Goldberg N, Fiedler A, Schwarz H (1994) Gas-phase generation and characterization of
nitrileimine, HCNNH: a new, stable isomer of diazomethane. Helv Chim Acta 77:2354–2362
38. Kiselev VG, Cheblakov PB, Gritsan NP (2011) Tautomerism and thermal decomposition of
tetrazole: high-level ab initio study. J Phys Chem A 115:1743–1753
39. Ríos-Gutiérrez M, Domingo LR (2019) The carbenoid-type reactivity of simplest nitrile imine
from a molecular electron density theory perspective. Tetrahedron 75:1961–1967
40. Granier M, Baceiredo A, Dartiguenave Y, Dartiguenave M, Menu MJ, Bertrand G (1990)
Synthesis and reactivity of stable phosphorus-substituted nitrilimines. X-ray crystal structure
of C-[bis (diisopropylamino) thioxophosphoranyl]-N-[bis (diisopropylamino) phosphanyl]
nitrilimine. J Am Chem Soc 112:6277–6285
41. Réau R, Veneziani G, Dahan F, Bertrand G (1992) A straightforward synthesis of nitrilimines;
X-ray crystal structure of a nitrilimine stabilized by non-heteroatom substituents. Angew
Chemie Int Ed English 31:439–440
42. Fauré J-L, Réau R, Wong MW, Koch R, Wentrup C, Bertrand G (1997) Nitrilimines:
evidence for the allenic structure in solution, experimental and ab initio studies of the
barrier to racemization, and first diastereoselective [3 + 2]-cycloaddition. J Am Chem Soc
119:2819–2824