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U–C Bond Insertion, Ring-Opening, and C–H Activation in a Uranium Bis(diisopropylamino)cyclopropenylidene (BAC) Adduct

Journal Article · · Organometallics
 [1];  [2];  [3];  [2];  [2]
  1. Univ. of California, Santa Barbara, CA (United States); UCSB
  2. Univ. at Buffalo, NY (United States)
  3. Univ. of California, Santa Barbara, CA (United States)
+ Show Author Affiliations
Reaction of [U(NR2)3] (R = SiMe3) with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in Et2O results in the formation of [(NR2)3U(BAC)] (1), which can be isolated in modest yields. Thermolysis of 1 in C6D6 at 85 °C results in the formation of the ring-opened U(IV) product, [(NR2)2U{N(R)(SiMe2CH=C(NiPr2)C(NiPr2)=CH)}] (2), which can be isolated in low yields. Mechanistic studies suggest that the formation of 2 proceeds via dissociation of BAC from 1 to regenerate [U(NR2)3], which converts into [U{N(R)(SiMe2CH2)}(NR2)2] at the elevated temperatures. BAC then inserts into the U–C bond of [U{N(R)(SiMe2CH2)}(NR2)2] to generate a cyclopropenyl intermediate, which undergoes ring opening and C–H activation to afford the final product, 2. We hypothesize that the ring-opening generates an unobserved carbene intermediate. Notably, thermolysis of a 1:1 mixture of independently prepared [U{N(R)(SiMe2CH2)}(NR2)2] and BAC results in clean formation of 2, providing strong support for the proposed mechanism. The formulations of both 1 and 2 were confirmed by X-ray crystallography. Finally, theoretical calculations indicate that the hypothesized uranium carbene intermediate features strong U–C bonding, potentially with some carbyne character in the electronic structure.
Research Organization:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0001136; SC0001861
OSTI ID:
2340725
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 10 Vol. 42; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Uranium
carbene compounds
ligands
mixtures
quantum mechanics