A Facile Route to Phosphanylborohydrides:Synthesis, Crystal Structure and Spectroscopic Properties of 1,2-Bis(Diphenylphosphinoborane)Ethane

Leyla Tatar Yildirim, Mehdi Masjedi, Saim Özkar

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DOI: 10.4236/jcpt.2011.11001                

Abstract

A novel and simple synthetic way using NaBH₄ in the mixure of H₂O-THF was applied to prepare 1,2-bis(diphenylphosphinoborane)ethane, dppe(BH₃)₂, in high yield and purity. The phosphanylborohydride compound dppe(BH₃)₂ was isolated in the form of colorless crystals and characterized by single crystal X-ray diffraction, ¹H, ¹³C, ³¹P and ¹¹B NMR spectroscopy. Prismatic colorless crystals of dppe(BH3)2 were obtained in monoclinic crystal system and space group P21 with two asymmetric units in the unit cell. Lattice parameters were: a = 11.657(2), b = 17.237(2), c = 12.764(2) Å, β = 98.735(14)°, 2535.0(7) ų

Keywords

Crystal Structure, Synthesis, Phosphinoborane, Sodium Borohydride, Phosphanylborohydride, X-Ray Diffraction

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	M. Masjedi, T. Demiralp and S. Ozkar, “Testing Catalytic Activity of Ruthenium (III) Acetylacetonate in the Presence of Trialkylphosphite or Trialkylphosphine in Hydrogen Generation from the Hydrolysis of Sodium Borohydride,” Journal of Molecular Catalysis A: Chemical, Vol. 310, No. 1-2, 2009, pp. 59-63. doi:10.1016/j.molcata.2009.05.022
[2]	K. C. Nainan and G. E. Ryschkewitsch, “A New Synthesis of AMINE- and Phosphine-Boranes,” Inorganic Chemistry, Vol. 8, No. 12, 1969, pp. 2671-2674. doi:10.1021/ic50082a027
[3]	O. Stephan, N. Riegel and S. Juge, “Polypyrrole Bearing Diphosphine Borane Groups: A New Way to Prepare Polymer-Supported Phosphine Ligands. Application to Palladium Catalysed Reactions,” Journal of Electroanalytical Chemistry, Vol. 421, No. 1-2, 1997, pp. 5-8. doi:10.1016/S0022-0728(96)01027-3
[4]	F. Dornhaus, M. Bolte, H-W. Lerner and M. Wagner, “The First Bidentate Phosphanylborohydrides: Synthesis, Structure and Reactivity Towards [CpFe(CO)2I],” Journal of Organometallic Chemistry, Vol. 692, No. 14, 2007, pp. 2949-2955. doi:10.1016/j.jorganchem.2007.03.006
[5]	R. A. Geanangel, “The Reaction of Amine and Phosphine Oxides with Diborane,” Journal of Inorganic and Nuclear Chemistry, Vol. 36, No. 6, 1974, pp. 1397-1398. doi:10.1016/0022-1902(74)80085-0
[6]	G. Jugie, J. P. Laussac and J. P. Laurent, “Addition Compounds of Trialkylphosphines (R3P) with Bromoboranes or Bromochloroboranes,” Bulletin de la Societe Chimique de France, Vol. 7, 1970, pp. 2542-2544.
[7]	S. Juge, M. Stephan, J. A. Laffitte and J. P. Genet, “Efficient Asymmetric Synthesis of Optically Pure Tertiary Mono and Diphosphine Ligands,” Tetrahedron Letters, Vol. 31, No. 44, 1990, pp. 6357-6360. doi:10.1016/S0040-4039(00)97063-1
[8]	S. Juge, M. Stephan, R. Merdes, J. P. Genet and S. Halut-Desportes, “Stereochemistry of the P-C Bond Formation in an Oxazaphospholidine Borane Complex,” ChemInform, 1993, pp. 531-533.
[9]	B. E. Kaloun, R. Merdes, J. P. Genet, J. Uziel and S. Juge, “Asymmetric Synthesis of (S,S)-(+)-1,1'-bis-(Methylphenyl-Phosphino) Ferrocene,” Journal of Organometallic Chemistry, Vol. 529, No. 1-2, 1997, pp. 455-463. doi:10.1016/S0022-328X(96)06690-9
[10]	H. Schmidbaur, M. Sigl and A. Schier, “Synthesis and Structure of Cyclic Phosphine-Boranes,” Journal of Organometallic Chemistry, Vol. 529, No. 1-2, 1997, pp. 323-327. doi:10.1016/S0022-328X(96)06616-8
[11]	R. Nunez, C. Vinas, F. Teixidor, R. Sillanpaa and R. Kivekas, “Phosphine-Boranes Incorporating the Carborane Cluster,” Journal of Organometallic Chemistry, Vol. 657, No. 1-2, 2002, pp. 224-231. doi:10.1016/S0022-328X(02)01326-8
[12]	J. A. Baban and B. P. Roberts, “Homolytic Reactions of Ligated Boranes. Part 3. Electron Spin Resonance Studies of Radicals Derived from Dialkyl-Amine Boranes,” Journal of the Chemical Society, Perkin Transactions 2, Vol. 10, 1986, pp. 1607-1611. doi:10.1039/p29860001607
[13]	H. Schmidbaur, G. Mueller and G. Blaschke, “Darstellung und Eigenschaften Einfacher und Stark Sterisch Gehinderter Phosphanalkylenborane,” Chemische Berichte, Vol. 113, No. 4, 1980, pp. 1480-1486. doi:10.1002/cber.19801130427
[14]	F. Dornhaus, M. Bolte, H.-W. Lerner and M. Wagner, “Phosphanylborohydrides: First Assessment of the Relative Lewis Basicities of [BH3PPh2]-, CH3PPh2 and HPPh2,” European Journal of Inorganic Chemistry, Vol. 2006, No. 9, 2006, pp. 1777-1785. doi:10.1002/ejic.200501126
[15]	F. Dornhaus, M. Bolte, H-W. Lerner and M. Wagner, “A Comparative Study of Chalcogenated Phosphanylborohydrides [EPR2BH3]- (R = Ph, tBu) and Triorganophosphane Chalcogenides EPPh2CH3 (E = O, S, Se, Te),” European Journal of Inorganic Chemistry, 2006, pp. 5138-5147. doi:10.1002/ejic.200600753
[16]	S. Sayalero and M. A. Pericas, “Work-up-Free Deprotection of Borane Complexes of Phosphines, Phosphites and Phosphinites with Polymer-Supported Amines,” Synlett, Vol. 16, 2006, pp. 2585-2588.
[17]	W. Angerer, W. S. Scheldrick and W. Malisch, “Ubergangsmetallsubstituierte Phosphane, Arsane und Stibane, XLVI, Einige Reaktionen des Ferrio-Phosphanes C5Me5(CO)2 Fe-PPh2 und Molekulstruktur Seines Boran-Addukts,” Chemische Berichte, Vol. 118, 1985, pp. 1261-1266. doi:10.1002/cber.19851180339
[18]	D. A. Hoic, W. M. Davis and G. C. Fu, “Diphenylphosphidoboratabenzene: An Anionic Analogue of Triphenylphosphine,” Journal of the American Chemical Society, Vol. 118, 1996, pp. 8176-8177. doi:10.1021/ja9615740
[19]	A.-C. Gaumont, M. B. Hursthouse, S. J. Coles and J. M. Brown, “Isolation of the Reactive Intermediate in Palladium-Catalysed Coupling of Secondary Phosphine-Boranes with Aryl Halides,” Chemical Communications, Vol. 1, 1999, pp. 63-64. doi:10.1039/a807830k
[20]	H. Dorn, C. A. Jaska, R. A. Singh, A. J. Lough and I. Manners, “Synthesis and Novel Reactivity of Platinum Phosphine-Borane Complexes trans-[PtH(PPhR.BH3) (PEt3)2] (R = H, Ph),” Chemical Communications, Vol. 12, 2000, pp. 1041-1042. doi:10.1039/b002615h
[21]	G. Muller and J. Brand, “Mono(Borane)Phosphides as Ligands to Lithium and Aluminum,” Organometallics, Vol. 22, 2003, pp. 1463-1467. doi:10.1021/om0209430
[22]	C. A. Jaska, A. J. Lough and I. Manners, “Linear Hybrid Aminoborane/Phosphinoborane Chains: Synthesis, Proton-Hydrid Interactions and Thermolysis Behavior,” Inorganic Chemistry, Vol. 43, No. 3, 2004, pp. 1090-1099.
[23]	Enraf-Nonius, “CAD-4 EXPRESS,” Enraf-Nonius, Delft, 1994.
[24]	K. Harms and S. Wocadlo, “XCAD4,” University of Marburg, Marburg, 1995.
[25]	G. M. Sheldrick, “A Short History of SHELX,” Acta Crystallographica, Vol. A64, 2008, pp. 112-122.
[26]	L. J. Farrugia, “XRDIFF: Simulation of X-Ray Diffraction Patterns,” Journal of Applied Crystallography, Vol. 30, No. 5-1, 1997, pp. 565-566.
[27]	A. L. Spek, “Single-Crystal Structure Validation with the Program PLATON,” Journal of Applied Crystallography, Vol. 36, No. 1, 2003, pp. 7-13. doi:10.1107/S0021889802022112
[28]	R. K. Harris, “Comments on N. M. R. Spectra of the XnAA’Xn’ Type,” Canadian Journal of Chemistry, Vol. 42, No. 10, 1964, pp. 2275-2281. doi:10.1139/v64-334