FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W1985755999> ?p ?o ?g. }

• W1985755999 endingPage "15456" @default.
• W1985755999 startingPage "15440" @default.
• W1985755999 abstract "A combined experimental/quantum chemical investigation of the transition metal-mediated dehydrocoupling reaction of H3B·NMe2H to ultimately give the cyclic dimer [H2BNMe2]2 is reported. Intermediates and model complexes have been isolated, including examples of amine−borane σ-complexes of Rh(I) and Rh(III). These come from addition of a suitable amine−borane to the crystallographically characterized precursor [Rh(η6-1,2-F2C6H4)(PiBu3)2][BArF4] [ArF = 3,5-(CF3)2C6H3]. The complexes [Rh(η2-H3B·NMe3)(PiBu3)2][BArF4] and [Rh(H)2(η2-H3B·NHMe2)(PiBu3)2][BArF4] have also been crystallographically characterized. Other intermediates that stem from either H2 loss or gain have been characterized in solution by NMR spectroscopy and ESI-MS. These complexes are competent in the catalytic dehydrocoupling (5 mol %) of H3B·NMe2H. During catalysis the linear dimer amine−borane H3B·NMe2BH2·NHMe2 is observed which follows a characteristic intermediate time/concentration profile. The corresponding amine−borane σ-complex, [Rh(PiBu3)2(η2-H3B·NMe2BH2·NHMe2)][BArF4], has been isolated and crystallographically characterized. A Rh(I) complex of the final product, [Rh(PiBu3)2{η2-(H2BNMe2)2}][BArF4], is also reported, although this complex lies outside the proposed catalytic cycle. DFT calculations show that the first proposed dehydrogenation step, to give H2B═NMe2, proceeds via two possible routes of essentially the same energy barrier: BH or NH activation followed by NH or BH activation, respectively. Subsequent to this, two possible low energy routes that invoke either H2/H2B═NMe2 loss or H2B═NMe2/H2 loss are suggested. For the second dehydrogenation step, which ultimately affords [H2BNMe2]2, a number of experimental observations suggest that a simple intramolecular route is not operating: (i) the isolated complex [Rh(PiBu3)2(η2-H3B·NMe2BH2·NHMe2)][BArF4] is stable in the absence of amine−boranes; (ii) addition of H3B·NMe2BH2·NHMe2 to [Rh(PiBu3)2(η2-H3B·NMe2BH2·NHMe2)][BArF4] initiates dehydrocoupling; and (iii) H2B═NMe2 is also observed during this process." @default.
• W1985755999 created "2016-06-24" @default.
• W1985755999 creator A5007726188 @default.
• W1985755999 creator A5012634256 @default.
• W1985755999 creator A5031577471 @default.
• W1985755999 creator A5042655264 @default.
• W1985755999 creator A5043954606 @default.
• W1985755999 date "2009-09-28" @default.
• W1985755999 modified "2023-10-16" @default.
• W1985755999 title "Monomeric and Oligomeric Amine−Borane σ-Complexes of Rhodium. Intermediates in the Catalytic Dehydrogenation of Amine−Boranes" @default.
• W1985755999 cites W1964090571 @default.
• W1985755999 cites W1968569727 @default.
• W1985755999 cites W1969019090 @default.
• W1985755999 cites W1970265568 @default.
• W1985755999 cites W1975071171 @default.
• W1985755999 cites W1975217371 @default.
• W1985755999 cites W1980690337 @default.
• W1985755999 cites W1983026194 @default.
• W1985755999 cites W1983979515 @default.
• W1985755999 cites W1986735880 @default.
• W1985755999 cites W1988091937 @default.
• W1985755999 cites W1989441552 @default.
• W1985755999 cites W1990108593 @default.
• W1985755999 cites W1993391523 @default.
• W1985755999 cites W1993499829 @default.
• W1985755999 cites W1997400705 @default.
• W1985755999 cites W1997606477 @default.
• W1985755999 cites W1998811239 @default.
• W1985755999 cites W2000466466 @default.
• W1985755999 cites W2002283452 @default.
• W1985755999 cites W2002501218 @default.
• W1985755999 cites W2004054543 @default.
• W1985755999 cites W2009202316 @default.
• W1985755999 cites W2013731046 @default.
• W1985755999 cites W2014073120 @default.
• W1985755999 cites W2015101049 @default.
• W1985755999 cites W2015723183 @default.
• W1985755999 cites W2017914721 @default.
• W1985755999 cites W2018270047 @default.
• W1985755999 cites W2018545745 @default.
• W1985755999 cites W2019534119 @default.
• W1985755999 cites W2021077383 @default.
• W1985755999 cites W2024018953 @default.
• W1985755999 cites W2025026758 @default.
• W1985755999 cites W2025719613 @default.
• W1985755999 cites W2027220992 @default.
• W1985755999 cites W2031497013 @default.
• W1985755999 cites W2032304951 @default.
• W1985755999 cites W2032719166 @default.
• W1985755999 cites W2033990154 @default.
• W1985755999 cites W2034810901 @default.
• W1985755999 cites W2040674498 @default.
• W1985755999 cites W2040718824 @default.
• W1985755999 cites W2041086195 @default.
• W1985755999 cites W2041086523 @default.
• W1985755999 cites W2046412723 @default.
• W1985755999 cites W2049379873 @default.
• W1985755999 cites W2050915803 @default.
• W1985755999 cites W2051613577 @default.
• W1985755999 cites W2054352523 @default.
• W1985755999 cites W2059020082 @default.
• W1985755999 cites W2059381386 @default.
• W1985755999 cites W2062586228 @default.
• W1985755999 cites W2062930697 @default.
• W1985755999 cites W2064167617 @default.
• W1985755999 cites W2066847471 @default.
• W1985755999 cites W2067674643 @default.
• W1985755999 cites W2069589915 @default.
• W1985755999 cites W2071187844 @default.
• W1985755999 cites W2072357435 @default.
• W1985755999 cites W2072780567 @default.
• W1985755999 cites W2080182825 @default.
• W1985755999 cites W2082004224 @default.
• W1985755999 cites W2082101197 @default.
• W1985755999 cites W2082323169 @default.
• W1985755999 cites W2086069085 @default.
• W1985755999 cites W2092006330 @default.
• W1985755999 cites W2093088840 @default.
• W1985755999 cites W2107471631 @default.
• W1985755999 cites W2115059637 @default.
• W1985755999 cites W2115926823 @default.
• W1985755999 cites W2124546133 @default.
• W1985755999 cites W2124786767 @default.
• W1985755999 cites W2127595119 @default.
• W1985755999 cites W2127615676 @default.
• W1985755999 cites W2131350133 @default.
• W1985755999 cites W2141921266 @default.
• W1985755999 cites W2157158629 @default.
• W1985755999 cites W2160505354 @default.
• W1985755999 cites W2163074701 @default.
• W1985755999 cites W2166689829 @default.
• W1985755999 cites W2168242144 @default.
• W1985755999 cites W2170284190 @default.
• W1985755999 cites W2319659394 @default.
• W1985755999 cites W2331402506 @default.
• W1985755999 cites W2518816332 @default.
• W1985755999 cites W4242347576 @default.
• W1985755999 cites W4249321870 @default.

• next