New triplet silylenes M–Si–M′–X along with some unusual cyclic forms (M = Li, Na, and K; M′ = Be, Mg, and Ca; X = F, Cl, and Br)
Comparison of 54 M-Si--M′′-X species is carried out using quantum mechanical ab initio and DFT computations at B3LYP/6-311++++G**, QCISD(T)/6-311++++G**, and CCSD(T)/6-311++++G** levels of theory (M = Li, Na, K; M′′ = Be, Mg, Ca, and X = F, Cl, Br). All triplet species with M = K appear more linear than their corresponding ones with Li and Na. The electronegativity reactivity descriptor for each halogen (X = F, Cl, Br) is used as a tool to evaluate the interrelated properties of these silylenes. Stability, assumed as singlet-triplet energy difference (ΔES−T)ΔES−T) for each series depends on the substituent's electropositivity, analyzed by applying appropriate isodesmic reactions. Stability of triplet M--Si-M′′-X silylenes increases as functions of electropositivity of αα-substituents and of ββ-substituents. The purpose of the present work was therefore to assess the influence of different di-alkaline metals with different ββ-substituents on the singlet--triplet energy gaps.
___
- Schoeller, W. W.; Sundermann, A.; Reiher, M.
Inorg. Chem.
1999
,
38
, 29-37.
- Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G.
Chem. Rev.
2000
,
100
, 39-92.
- Mizuhata, Y.; Sasamori, T.; Tokitoh, N.
Chem. Rev.
2009
,
109
, 3479-3511.
- Sasamori, T.; Tokitoh, N. in
Encyclopedia of Inorganic Chemistry II
; King, R. B., Eds. John Wiley & Sons:
Chichester, UK, 2005, pp. 1698-1740.
- Fueno, T. Eds.
The Transition State: A Theoretical Approach
; Gordon and Breach Science Publishers: Langhorne,
PA USA, 1999, pp. 147-161.
- Barden, C. J.; Schaefer, H. F.
J. Chem. Phys.
2000
,
112
, 6515-6516.
- Lee, E. P. F.; Dyke, J. M.; Wright, T. G.
Chem. Phys. Lett.
2000
,
326
, 143-150.
- Bruce, M.
Chem. Rev.
1991
,
91
, 197-257.
- Apeloig, Y. in
The Chemistry of Organic Silicon Compounds
; Patai, S.; Rappoport, Z. Eds. Vol. 1, Wiley: New
York, NY, USA, 1989, p. 57.
- Vessally, E.
Heteroa. Chem.
2008
,
19
, 245-251.
- Schaefer, H. F.
Science
1986
,
231
, 1100-1107.
- Holthausen, M. C.; Koch, W.; Apeloig, Y.
J. Am. Chem. Soc.
1999
,
121
, 2623-2624.
- Sekiguchi, A.; Tanaka, T.; Ichinohe, M.; Akiyama, K.; Gaspar, P. P.
J. Am. Chem. Soc.
2008
,
130
, 426-427.
- Grev, R. S.; Schaefer, H. F.; Gaspar, P. P.
J. Am. Chem. Soc.
1991
,
113
, 5638-5643.
- Luke, B. T.; Pople, J. A.; Krogh-Jespersen, M. B.; Apeloig, Y.; Karni, M.; Chandrasekhar, J.; Schleyer, P. v. R.
J. Am. Chem. Soc.
1986
,
108
, 270-284.
- Kalcher, J.; Sax, A. F.
J. Mol. Struct. (THEOCHEM)
1992, 253, 287-302.
- Krogh-Jespersen, K.
J. Am. Chem. Soc.
1985
,
107
, 537-543.
- Colvin, M. E.; Schaefer, H. F.; Bicerano, J.
J. Chem. Phys.
1985
,
83
, 4581-4584.
- Inoue, Sh.; Ichinohe, M.; Sekiguchi, A.
Organometallics
2008
,
27
, 1358-1360.
- Nefedov, O. M.; Egorov, M. P.; Ioffe, A. I.; Menchikov, L. G.; Zuev, P. S.; Minkin, V. I.; Simkin, Ya. B.; Glukhovtsev,
M. N.
Pure Appl. Chem.
1992
,
64
, 265-314.
- Schwartz, R. L.; Davico, G. E.; Ramond, T. M.; Lineberger, W. C.
J. Phys. Chem.
1999
,
103
, 8213-8221.
- Zhu, Z.; Bally, T.; Stracener, L. L.; McMahon, R. J.
J. Am. Chem. Soc.
1999
,
121
, 2863-2874.
- Wang, Y.; Yuzawa, T.; Hamaguchi, H.; Toscano, J. P.
J. Am. Chem. Soc.
1999
,
121
, 2875-2882.
- Wang, Y.; Toscano, J. P.
J. Am. Chem. Soc.
2000
,
122
, 4512-4513.
- Gordon, M. S.
Chem. Phys. Lett.
1985
,
114
, 348-352.
- Kassaee, M. Z.; Musavi, S. M.; Ghambarian, M.
J. Organomet. Chem.
2006
,
691
, 1845-1856.
- Razuvaev, G. A.; Gribov, B. G.; Domrachev, G. A.; Salamatin, B. A. In
Metalloorganicheskie soedineniya v
elektronike (Organometallic Compounds in Electronics)
, Nauka: Moscow, USSR, 1972.
- Gribov, B. G.; Domrachev, G. A.; Zhuk, B. V.; Kaverin, B. S.; Kozyrkin, B. I.; Mel’nikov, V. V.; Suvorova, O. N.
In
Precipitation of Films and Covers by Decomposition of Metalloorganic Compounds
. Moscow, USSR: Science,
1981, p. 322.
- Kassaee, M. Z.; Buazar, F.; Soleimani-Amiri, S.
J. Mol. Struct. (THEOCHEM)
2008
, 866, 52-57.
- Kendall, R. A.; Jr. Dunning, T. H.; Harrison, R. J. J.
Chem. Phys.
1992
,
96
, 6796-6806.
- Yan, Z.; Truhlar, D. G.
Theor. Chem. Account.
2008
,
120
, 215-241.
- Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A.
Ab Initio Molecular Orbital Theory
. John Wiley and
Sons: New York, NY, USA, 1986.
- Becke, A. D.
Phys. Rev.
1988
,
38
, 3098.
- Becke, A. D.
J. Chem. Phys.
1993
,
98
, 5648-5652.
- Lee, C.; Yang, W.; Parr, R. G.
Phys. Rev.
1988
,
37
, 785.
- Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga,
N.; Nguyen, K. A.; Su, S. J.; et al.
J. Comput. Chem.
1993
,
14
, 1347-1363.
- Sobolewski, A. L.; Domcke, W.
J. Phys. Chem. A
2002
,
106
, 4158-4167.
- Parr, R. G.; Yang, W.
Density Functional Theory of Atoms and Molecules.
Oxford University Press: New York,
NY, USA, 1989.
- Hoffmann, R.; Schleyer, P. v. R.; Schaefer. H. F.
Angew. Chem. Int. Ed.
2008
,
47
, 7164-7167.
- Sulzbach, H. M.; Bolton, E.; Lenoir, D.; Schleyer, P. v. R.; Schaefer, H. F.
J. Am. Chem. Soc.
1996
,
118
, 9908-9914.
- Bundhun, A.; Abdallah, H. H.; Ramasami, P.; Schaefer, H. F.
J. Phys. Chem. A
2010
,
114
, 13198-13212.
- Ward, S. G.; Taylor, R. C. In
Metal-Based Anti-Tumor Drugs
; Gielen, M. F. Ed., Freund Publ.: London, UK, 1988.
- Burgert, B.; Driess, M. In
Functional Molecular Silicon Compounds II
. Springer International Publishing: New
York, NY, USA, 2013, pp. 85-123.
- Moss, R. A.; Fantina, M. E.
J. Am. Chem. Soc.
1978
,
100
, 6788-6790.
- Nyíri, K. Szilvási, T.; Veszprémi, T.
Dalton Trans.
2010
,
39
, 9347-9352.