2012
DOI: 10.1002/chem.201102029
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Calcium–Amidoborane–Ammine Complexes: Thermal Decomposition of Model Systems

Abstract: Hydrocarbon-soluble model systems for the calcium-amidoborane-ammine complex Ca(NH(2)BH(3))(2)⋅(NH(3))(2) were prepared and structurally characterized. The following complexes were obtained by the reaction of RNH(2)BH(3) (R = H, Me, iPr, DIPP; DIPP = 2,6-diisopropylphenyl) with Ca(DIPP-nacnac)(NH(2))⋅(NH(3))(2) (DIPP-nacnac = DIPP-NC(Me)CHC(Me)N-DIPP): Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))(2), Ca(DIPP-nacnac)(NH(2)BH(3))⋅(NH(3))(3), Ca(DIPP-nacnac)[NH(Me)BH(3)]⋅(NH(3))(2), Ca(DIPP-nacnac)[NH(iPr)BH(3)]⋅(NH(3))(2… Show more

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Cited by 28 publications
(21 citation statements)
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“…Selected bond length and angle data and details of the X-ray analysis are again provided in Tables 2–4 respectively. The alkaline earth centres of compound 5 are connected through bridging interactions provided by both oxygen atoms of a [H 2 Bpin] – anion, in a manner reminiscent of that observed in both a previously reported trimeric calcium species, [LCa(H 2 Bpin)] 3 (where L is as defined in Scheme 3 ), 26 and a μ-Mg–H–Mg and O–B–O bridged β-diketiminato magnesium compound the connectivity of which was established through a low resolution ( R 1 = 10.31%) X-ray diffraction analysis. 16 Although each of the magnesium atoms displays a similar pseudo -tetrahedral N 3 O-coordination sphere, with ligation provided by the bridging borate and a single β-diketiminate anion, the nature of the fourth nitrogen-centred ligand differs across the two Mg centres of the molecule.…”
Section: Resultsmentioning
confidence: 84%
“…Selected bond length and angle data and details of the X-ray analysis are again provided in Tables 2–4 respectively. The alkaline earth centres of compound 5 are connected through bridging interactions provided by both oxygen atoms of a [H 2 Bpin] – anion, in a manner reminiscent of that observed in both a previously reported trimeric calcium species, [LCa(H 2 Bpin)] 3 (where L is as defined in Scheme 3 ), 26 and a μ-Mg–H–Mg and O–B–O bridged β-diketiminato magnesium compound the connectivity of which was established through a low resolution ( R 1 = 10.31%) X-ray diffraction analysis. 16 Although each of the magnesium atoms displays a similar pseudo -tetrahedral N 3 O-coordination sphere, with ligation provided by the bridging borate and a single β-diketiminate anion, the nature of the fourth nitrogen-centred ligand differs across the two Mg centres of the molecule.…”
Section: Resultsmentioning
confidence: 84%
“…Our own interest in this topic is motivated by the use of alkaline-earth (Ae) elements as non-toxic and inexpensive catalysts for the synthesis of inorganic polymers. 15,16 Following previous investigations into Ae-mediated catalytic and stoichiometric amine-borane dehydrogenation and dehydrocoupling, [17][18][19][20][21][22][23][24][25][26] we recently reported a series of β-diketiminate (BDI) supported alkaline-earth (Ae) phosphidoborane complexes, which are prepared by exposing diphenylphosphine-borane to readily accessible BDI-Ae hydride, alkyl, or amide precursors (Scheme 2a). 27 Attempts to achieve complete phosphine-borane dehydrogenation were unsuccessful, however, and the use of super-stoichiometric quantities of phosphine-borane resulted in BH 3 transfer to provide the phosphinodiboronate complex 2 and uncomplexed diphenylphosphine (Scheme 2a).…”
Section: Introductionmentioning
confidence: 99%
“…111,112 Hydrocarbon-soluble b-diketiminato model systems for the calcium-amidoborane-ammine system have also been prepared while a series of barium (N,N-dimethylamino)diboranates has also been described. 113,114 Several calcium bis(tetraethylaluminate) complexes with N-donor ligands have been reported. 115 Alkali and alkaline earth metals have been found to be efficiently activated in aromatic hydrocarbons or substituted 1,3-dienes to produce well-defined mononuclear diene complexes of calcium, strontium, and barium.…”
Section: Group 16 Donorsmentioning
confidence: 99%