title: Phosphaalkynes from acid chlorides via P for O(Cl) metathesis: a recyclable niobium phosphide (P(3-)) reagent that effects C-P triple-bond formation.
abstract: Reported herein is a new, metathetical P for O(Cl) exchange mediated by an anionic niobium phosphide complex that furnished phosphaalkynes (RCP) from acid chlorides (RC(O)Cl) under mild conditions. The niobaziridine hydride complex, Nb(H)(tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-Me2C6H3), has been shown previously to react with elemental phosphorus (P4), affording the mu-diphosphide complex, (mu2:eta2,eta2-P2)[Nb(N[Np]Ar)3]2, (2), which can be subsequently reduced by sodium amalgam to the anonic, terminal phosphide complex, [Na][PNb(N[Np]Ar)3] (3). It is now shown that treatment of 3 with either pivaloyl (t-BuC(O)Cl) or 1-adamantoyl (1-AdC(O)Cl) chloride provides the thermally unstable niobacyles, (t-BuC(O)P)Nb(N[Np]Ar)3 (4-t-Bu) and (1-AdC(O)P)Nb(N[Np]Ar)3 (4-1-Ad), which are intermediates along the pathway to ejection of the known phosphaalkynes t-BuCP (5-t-Bu) and 1-AdCP(5-1-Ad). Phosphaalkyne ejection from 4-t-Bu and 4-1-Ad proceeds with formation of the niobium(V) oxo complex ONb(N[Np]Ar)3 (6) as a stable byproduct. Preliminary kinetic measurements for fragmentation of 4-t-Bu to 5-t-Bu and 6 in C6D6 solution are consistent with a first-order process, yielding the thermodynamic parameters DeltaH = 24.9 +/- 1.4 kcal mol-1 and DeltaS = 2.4 +/- 4.3 cal mol-1 K-1 over the temperature range 308-338 K. Separation of volatile 5-t-Bu from 6 after thermolysis has been readily achieved by vacuum transfer in yields of 90%. Pure 6 is recovered after vacuum transfer and can be treated with 1.0 equiv of triflic anhydride (Tf2O, Tf = O2SCF3) to afford the bistriflate complex, Nb(OTf)2(N[Np]Ar)3 (7), in high yield. Complex 7 provides direct access to 1 upon reduction with magnesium anthracene, thus completing a cycle of element activation, small-molecule generation via metathetical P-atom transfer, and deoxygenative recycling of the final niobium(V) oxo product.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
authors.forename: Joshua S
authors.initials: JS
authors.lastname: Figueroa
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins