Page 10 - Interaction of Multiple Bonded and Unsaturated Heavier Main Group Compounds with Hydrogen, Ammonia, Olefins, and Related Molecules

Reactivity of Multiple Bonded and Main Group Compounds Power

that the addition of the nitrile Me 3 SiCN to his disilyne RSiSiR REFERENCES
i
(R = Si{CH(SiMe 3 ) 2 } 2 Pr ) gave the bis(isonitrile) adduct RSiSiR- 1 Fischer, R. C.; Power, P. P. π-Bonding and the Lone Pair Effect in Multiple Bonds Involving
Heavier Main Group Elements: Developments in the New Millennium. Chem. Rev. 2010,
(CNSiMe 3 ) 2 as a coproduct which probably arises from the 110,3877–3923.
existence of the Me 3 SiNC in equilibrium with Me 3 SiCN. 2 (a) Sekiguchi, A.; Kinjo, R.; Ichinohe, M. A Stable Compound Containing a Silicon-Silicon
TripleBond.Science 2004,305, 1755. (b) Stender, M.; Phillips, A. D.;Wright,R.J.;Power,
P. P. Synthesis and Characterization of a Digermanium Analogue of an Alkyne. Angew.
Chem., Int. Ed. 2002, 41, 1785–1787. (c) Phillips, A. D.; Wright, R. J.; Olmstead, M. M.;
6. Summary and Future Prospects Power,P.P.SynthesisandCharacterizationof2,6-Dipp 2 -H 3 C 6 SnSnC 6 H 3 -2,6-Dipp 2 (Dipp=
i
C 6 H 3 -2,6-Pr 2 ): A Tin Analogue of an Alkyne. J. Am. Chem. Soc. 2002, 124, 5930–
The stable multiple bonded and open shell species discussed 5931. (d) Pu, L.; Twamley, B.; Power, P. P. Synthesis and Characterization of 2,6-
above possess unique reactivity in many instances. The key Trip 2 H 3 C 6 PbPbC 6 H 3 -2,6-Trip 2 (Trip = C 6 H 2 -2,4,6-i-Pr 3 ): A Stable Heavier Group 14
Element Analogue of an Alkyne. J. Am. Chem. Soc. 2000, 122, 3524–3525. (e) Wiberg
t
to their isolation has been the use of terphenyl ligands which showed that the disilyne (R* 2 MeSi)SiSi(SiMeR 2 *) (R* = SiBu 3 ) could be generated in
29
solution and characterized spectroscopically ( Si NMR). See: Wiberg, N.; Niedermayer,
provide the steric hindrance necessary for stability but yet W.; Fischer, G.; N€ oth, H.; Suter, M. Synthesis Structure and Dehalogenation of the
allow access of many small molecules to the reactive cen- Disilene R(Cl)Si:Si(Cl)R [R = (tBu 3 Si) 2 MeSi]. Eur. J. Inorg. Chem. 2002, 1066–1070.
Wiberg, N.; Vasisht, S.K.; Fischer, G.; Mayer, P.A Relatively StableDisilyneRSitSiR(R=
ters. The reactions generally take place under ambient SiMe(SitBu) 2 ). Z. Anorg. Allg. Chem. 2004, 630,1823–1828.
conditions and proceed in near quantitative yield. In many 3 Olmstead, M. M.; Simons, R. S.; Power, P. P. SynthesisandCharacterization of [Sn 2 {C 6 H 3 -

2,6(2,4,6-i-Pr 3 C 6 H 2 ) 2 } 2 ] .: A Singly Reduced Valence Isomer of a “Distannyne. J. Am.
cases, the direct reactions, for example, those with hydrogen Chem. Soc. 1997, 119, 11705–11706.
5
4 Simons, R. S.;Power,P.P.(η -C 5 H 5 )(CO) 2 MoGeC 6 H 3 -2,6-Mes 2 : A Transition-Metal
or ammonia, provide the simplest and highest yielding
Germylyne Complex. J. Am. Chem. Soc. 1996, 118, 11966–11967.
routes to the respective hydride or amido products. The 5 Grev, R. S. Structure and Bonding in the Parent Hydrides and Multiply Bonded Silicon and
Germanium Compounds: from MH n to R 2 M:M R 2 and RMdM R. Adv. Organomet. Chem.
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discovery of reversible olefin and isocyanide complexation
1991, 33, 125–170.
as well as various isomerization equlibria involving heavier 6 Jung, Y.; Brynda, M.; Power, P. P.; Head-Gordon, M. Ab Initio Quantum Chemistry
Calculations on the Electronic Structure of Heavier Alkyne Congeners: Diradical Character
group 14 element derivatives show that the heavier main and Reactivity. J. Am. Chem. Soc. 2006, 128,7185–7192.
group species can engage in dynamic processes. This opens 7 Sugiyama, Y.; Sasamori, T.; Hosoi, Y.; Furukawa, Y.; Takagi, N.; Nagase, S.; Tokitoh, N.
Synthesis and Properties of a New Kinetically Stabilized Digermyne: New Insights for a
the possibility that these and related main group com- Germanium Analogue of an Alkyne. J. Am. Chem. Soc. 2006, 128, 1023.
pounds may have catalytic properties. A conspicuous aspect 8 Peng, Y.; Fischer,R. C.;Merrill, W. A.; Fischer,J.;Pu, L.;Ellis, B.D.; Fettinger,J.C.; Herber,
R. H.; Power, P. P. Substituent Effects in Ditetrel Alkyne Analogues: Multiple vs Single
of the compounds discussed in the Account has been the Bonded Isomers. Chem. Sci. 2010, 1, 461–468.
relatively few results for aluminum, 45 the most abundant 9 Takagi, N.; Nagase, S. Tin Analogues of Alkynes Multiply Bonded vs. Singly Bonded
Structures. Organometallics 2007, 26,469–471.
main group metal and the most important in the chemical
10 Power, P. P. Multiple Bonding between HeavierGroup 13 Elements. Structure and Bonding;
industry. Future developments relevant to the theme of this Atwood, D. A., Roesky, H. W., Eds.; Vol. 103: Group 13 Elements-Research Trends - Book
1; Springer-Verlag: Berlin, Heidelberg, 2002; pp 5784.
Account involving this metal may be anticipated.
11 Wang, Y. Z.; Robinson, G. H. Organometallics of the Group 13 M-M bond (M = Al, Ga or In)
and the Concept of Metalloaromacity. Organometallics 2007, 26,2–11.
12 Linti, G.; Schn€ ockel, H.; Uhl, W.; Wiberg, N. Clusters of the Heavier Group 13 Elements in
Molecular Clusters of the Main Group Elements;Driess, M., N€ oth, M., Eds.; Wiley:
BIOGRAPHICAL INFORMATION
New York, 2004; pp 126168.
Philip Power is a Distinguished Professor of Chemistry at the 13 Schumann, H.;Janiak, C.;G€ orlitz, F.;Loebel,J.;Dietrich, A. Synthesis and CrystalStructure
University of California, Davis. His main interests lie in the ex- of Pentabenzylcyclopentadienylindium(I). J. Organomet. Chem. 1989, 363, 243–251.
14 Haubrich, S. T.; Power, P. P. Monomeric InC 6 H 3 -2,6-Trip 2 (Trip = -C 6 H 2 -2,4,6-i-Pr 3 )and
ploratory synthesis of new main-group and transition-metal com- 5
ItsManganese Complex (η -C 5 H 5 )(CO) 2 MnInC 6 H 3 -2,6-Trip 2 : One-Coordinate Indium in the
plexes. A major theme of his work has been the use of sterically Solid State. J. Am. Chem. Soc. 1998, 120, 2202–2203.
crowded ligands to stabilize species with new type of bonding, low 15 (a)Wright, R. J.;Phillips, A. D.;Hardman,N.J.; Power, P. P. The “Diindene” ArInInAr (Ar =
i
coordination numbers, and high reactivity toward small molecules. C 6 H 3 -2,6-Dipp 2 , Dipp = C 6 H 3 -2,6-Pr 2 ). Dimeric versus Monomeric In(I) Aryls: para-
Substituent Effects in Terphenyl Ligands. J. Am. Chem. Soc. 2002, 124,8538–8539.
(b)Hardman, N. J.; Wright,R. J.; Phillips,A.D.;Power,P.P.SynthesisandCharacterizationof the
The author is indebted to many talented co-workers named in the Neutral“Digallene”Ar'GaGaAr'andItsReductiontoNa 2 Ar'GaGaAr'(Ar'=2,6-Dipp 2 C 6 H 3 ,Dipp=
i
2,6-Pr 2 C 6 H 3 ). Angew. Chem., Int. Ed. 2002, 41, 2842–2844.
references who performed the work described. Fruitful collabora- (c)Wright,R.J.;Phillips,A.D.;Hino,S.;Power,P.P.SynthesisandReactivityofDimericAr TlTlAr 0
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andTrimeric(Ar Tl) 3 (Ar ,Ar =BulkyTerphenylGroup) Thallium(I) Derivatives:Tl(I)-Tl(I) Bonding
tions with Dr. M. Brynda and the groups of Professors M. Head- in Species Ligated by Monodentate Ligands. J. Am. Chem. Soc. 2005, 127, 4794–4799.
Gordon, R. Herber, G. Merino, L. Pu, S. Nagase, and H. Tuononen are 16 Zhu, Z.; Guo,J. D.;Fischer,R. C.; Ellis, B.D.; Rivard, E.; Merrill,W. A.; Olmstead, M.M.;Pu,
L.; Nagase, S.; Power, P. P. Synthesis, Characterization and Real Molecule Calculations for
gratefully acknowledged. The synthesis and characterization of the Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds
multiple bonded heavy group 13 and 14 elements was originally in Digallenes and Digallynes. Chem.;Eur. J. 2009, 15, 5263–5272.
17 (a) Wright,R.J.;Phillips,A. D.; Power,P.P. The[2þ 4] Diels-AlderCycloadditonProductof
supported by the National Science Foundation. The reactivity of a Probable Dialuminene, Ar AlAlAr (Ar =C 6 H 3 - 2,6-Dipp 2 ;Dipp= C 6 H 3 -2,6-Pr 2 ), with
i
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Toluene. J. Am. Chem. Soc. 2003, 125,10784–19785. (b) Wright, R. J.; Fettinger, J. C.;
main group species toward small molecules has been supported by
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Power, P. P. Synthesis and Structure of the “Dialuminyne” Na 2 Ar AlAlAr and Na 2 (Ar Al) 3
i
the Department of Energy, Office of Basic Energy Sciences. (Ar =C 6 H 3 -2,6-(C 6 H 3 -2,6-Pr 2 ) 2 Ar =C 6 H 3 -2,6-(C 6 H 2 -2,4,6-Me 3 ) 2 : Al-Al Bonding in
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Al 2 Na 2 and Al 3 Na 2 and Clusters. Angew. Chem., Int. Ed. 2006, 45, 5953–5956.
18 Moilanen, J.; Power, P. P.; Tuononen, H. M. The Nature of the Bonding in Group 13
FOOTNOTES
Dimetallenes: A Balance between Static and Dynamic Electron Correlation Effects, Singlet
*Fax: 530-752-9463. E-mail: pppower@ucdavis.edu. Diradical Character. Inorg. Chem. 2010, 49, 10992–11000.
636 ’ ACCOUNTS OF CHEMICAL RESEARCH ’ 627–637 ’ 2011 ’ Vol. 44, No. 8