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Dinitrogen Reduction by Titanium PCP Complexes
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DOI：10.1021/acs.inorgchem.5c04909.png)
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Abstract
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Reduction of RPCP pincer-supported titanium dichloride (R = Cy 1a, t Bu 1b) under a N2 atmosphere affords the respective bridging dinitrogen complex [{(RPCP)TiCl}2{mu-N2}] (R = Cy 2a, t Bu 2b). N2 is bound in an end-on fashion in both 2a and 2b, though much stronger activation is observed in 2b, as evidenced by Raman spectroscopy. Surprisingly, 2a is paramagnetic, whereas 2b is diamagnetic. Exchanging the chloride for a methyl group in 2 affords [{(RPCP)TiMe}2{mu-N2}] (R = Cy 3a, t Bu 3b); both being diamagnetic and displaying equally strong N2 activation. The effect coordination sphere has on N2 activation was further investigated: halide abstraction of 2b yields cationic Ti(III) [{( tBuPCP)Ti(Et2O)}2(mu-N2)] [BArF 4]2 4; and reduction with 5% K/KI delivers a further reduced species 5. Complexes 1, 2, and 5 are capable of stoichiometric dinitrogen silylation.
Keywords:
MOLECULAR NITROGEN
SPECTROSCOPIC PROPERTIES
SIDE-ON
ACTIVATION
CRYSTAL
FUNCTIONALIZATION
COORDINATION
CHEMISTRY
CLEAVAGE
AFFINITY
Journal
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4.7
Papers:
4.9W
Citations:
10.5W
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Cited Papers
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