We report here a “nonspectator” behavior for an unsupported
We report here a “nonspectator” behavior for an unsupported
- NSF-PAR ID:
- 10117790
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 58
- Issue:
- 42
- ISSN:
- 1433-7851
- Format(s):
- Medium: X Size: p. 15005-15009
- Size(s):
- p. 15005-15009
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract L ‐function σ3‐P ligand (i.e. P{N[o ‐NMe‐C6H4]2},1a ) in complex with the cyclopentadienyliron dicarbonyl cation (Fp+). Treatment of1a ⋅Fp+with [(Me2N)3S][Me3SiF2] results in fluoride addition to theP ‐center, giving the isolable crystalline fluorometallophosphorane1aF ⋅Fp that allows a crystallographic assessment of the variance in the Fe−P bond as a function of P‐coordination number. The nonspectator reactivity of1a ⋅Fp+is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me2N)3P⋅Fp+(i.e.1b ⋅Fp+), which is inert to fluoride addition. These observations establish a nonspectator L/X‐switching in (σ3‐P)–M complexes by reversible access to higher‐coordinate phosphorus ligand fragments. -
Abstract Low‐temperature reaction of the tris(pyrazolyl)borate copper(II) hydroxide [iPr2TpCu]2(μ‐OH)2with triphenylsilane under a dinitrogen atmosphere gives the bridging dinitrogen complex [iPr2TpCu]2(μ‐1,2‐N2) (
3 ). X‐ray crystallography reveals an only slightly activated N2ligand (N‐N: 1.111(6) Å) that bridges between two monovalentiPr2TpCu fragments. While DFT studies of mono‐ and dinuclear copper dinitrogen complexes suggest weak π‐backbonding between the d10CuIcenters and the N2ligand, they reveal a degree of cooperativity in the dinuclear Cu‐N2‐Cu interaction. Addition of MeCN, CNAr2,6‐Me, or O2to3 releases N2with formation ofiPr2TpCu(L) (L=NCMe, CNAr2,6‐Me2) or [iPr2TpCu]2(μ‐η2:η2‐O2) (1 ). Addition of triphenylsilane to [iPr2TpCu]2(μ‐OH)2in pentane allows isolation of a key intermediate [iPr2TpCu]2(μ‐H) (5 ). Although5 thermally decays under N2to give3 , it reduces unsaturated substrates, such as CO and HC≡CPh to HC(O)H and H2C=CHPh, respectively. -
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). -
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). -
Abstract Decarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO−, to the NbIVcomplex [(PNP)NbCl2(N
t BuAr)] (1 ) (PNP=N[2‐Pi Pr2‐4‐methylphenyl]2−; Ar=3,5‐Me2C6H3) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(Nt BuAr)] (2 ). Reduction of2 with CoCp*2cleaves the P−P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(Nt BuAr)] (3 ). Theoretical studies have been used to understand both the coupling of the P‐atom and the reductive cleavage of the P−P bond. Reaction of3 with a two‐electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P−P coupled ligand, namely [(PNPP)Nb=S(Nt BuAr)] (4 ).