Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(
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Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(
- NSF-PAR ID:
- 10474444
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 135
- Issue:
- 50
- ISSN:
- 0044-8249
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The “masked” terminal Zn sulfide, [K(2.2.2‐cryptand)][MeLZn(S)] (
2 ) (MeL={(2,6‐iPr2C6H3)NC(Me)}2CH), was isolated via reaction of [MeLZnSCPh3] (1 ) with 2.3 equivalents of KC8in THF, in the presence of 2.2.2‐cryptand, at −78 °C. Complex2 reacts readily with PhCCH and N2O to form [K(2.2.2‐cryptand)][MeLZn(SH)(CCPh)] (4 ) and [K(2.2.2‐cryptand)][MeLZn(SNNO)] (5 ), respectively, displaying both Brønsted and Lewis basicity. In addition, the electronic structure of2 was examined computationally and compared with the previously reported Ni congener, [K(2.2.2‐cryptand)][tBuLNi(S)] (tBuL={(2,6‐iPr2C6H3)NC(tBu)}2CH). -
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Abstract The “masked” terminal Zn sulfide, [K(2.2.2‐cryptand)][MeLZn(S)] (
2 ) (MeL={(2,6‐iPr2C6H3)NC(Me)}2CH), was isolated via reaction of [MeLZnSCPh3] (1 ) with 2.3 equivalents of KC8in THF, in the presence of 2.2.2‐cryptand, at −78 °C. Complex2 reacts readily with PhCCH and N2O to form [K(2.2.2‐cryptand)][MeLZn(SH)(CCPh)] (4 ) and [K(2.2.2‐cryptand)][MeLZn(SNNO)] (5 ), respectively, displaying both Brønsted and Lewis basicity. In addition, the electronic structure of2 was examined computationally and compared with the previously reported Ni congener, [K(2.2.2‐cryptand)][tBuLNi(S)] (tBuL={(2,6‐iPr2C6H3)NC(tBu)}2CH). -
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Abstract The trichromium cluster (tbsL)Cr3(thf) ([tbsL]6−=[1,3,5‐C6H9(NC6H4‐
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Abstract The trichromium cluster (tbsL)Cr3(thf) ([tbsL]6−=[1,3,5‐C6H9(NC6H4‐
o ‐NSit BuMe2)3]6−) exhibits steric‐ and solvation‐controlled reactivity with organic azides to form three distinct products: reaction of (tbsL)Cr3(thf) with benzyl azide forms a symmetrized bridging imido complex (tbsL)Cr3(μ 3‐NBn); reaction with mesityl azide in benzene affords a terminally bound imido complex (tbsL)Cr3(μ 1‐NMes); whereas the reaction with mesityl azide in THF leads to terminal N‐atom excision from the azide to yield the nitride complex (tbsL)Cr3(μ 3‐N). The reactivity of this complex demonstrates the ability of the cluster‐templating ligand to produce a well‐defined polynuclear transition metal cluster that can access distinct single‐site and cooperative reactivity controlled by either substrate steric demands or reaction media.
