Protonation Studies of a Tungsten Dinitrogen Complex Supported by a Diphosphine Ligand Containing a Pendant Amine

Autor:	Monte L. Helm, R. Morris Bullock, Charles J. Weiss, Shentan Chen, Michael T. Mock, Jonathan D. Egbert
Rok vydání:	2014
Předmět:	Hydride Ligand Organic Chemistry chemistry.chemical_element Protonation Tungsten Medicinal chemistry Catalysis Inorganic Chemistry Ammonia chemistry.chemical_compound chemistry Organic chemistry Amine gas treating Physical and Theoretical Chemistry Triflic acid
Zdroj:	Organometallics. 33:2189-2200
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om401127v
Popis:	Treatment of trans-[W(N2)2(dppe)(PEtNMePEt)] (dppe = Ph2PCH2CH2PPh2; PEtNMePEt = Et2PCH2N(Me)CH2PEt2) with 3 equiv of tetrafluoroboric acid (HBF4·Et2O) at −78 °C generated the seven-coordinate tungsten hydride trans-[W(N2)2(H)(dppe)(PEtNMePEt)][BF4]. At higher temperatures, protonation of a pendant amine is also observed, affording trans-[W(N2)2(H)(dppe)(PEtNMe(H)PEt)][BF4]2, with formation of the hydrazido complex [W(NNH2)(dppe)(PEtNMe(H)PEt)][BF4]2 as a minor product. A similar product mixture was obtained using triflic acid (HOTf). The protonated products are thermally sensitive and do not persist at ambient temperature. Upon acid addition to the carbonyl analogue cis-[W(CO)2(dppe)(PEtNMePEt)], the seven-coordinate carbonyl hydride complex trans-[W(CO)2(H)(dppe)(PEtNMe(H)PEt)][OTf]2 was generated. A mixed diphosphine complex without the pendant amine in the ligand backbone, trans-[W(N2)2(dppe)(depp)] (depp = Et2P(CH2)3PEt2), was synthesized and treated with HOTf, selectively generating a hydrazido comp...
Databáze:	OpenAIRE
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