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An Unexpected Staudinger Reaction at an N-Heterocyclic Carbene-Carbon Center

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An Unexpected Staudinger Reaction at an N-Heterocyclic Carbene-Carbon Center Canadian Journal of Chemistry An Unexpected Staudinger Reaction at an N-Heterocyclic Carbene-carbon Center Journal: Canadian Journal of Chemistry Manuscript ID cjc-2017-0607.R1 Manuscript Type: Article Date Submitted by the Author: 08-Jan-2018 Complete List of Authors: Roy, Matthew; University of Alberta Department of Chemistry Miao, Linkun; University of Alberta Department of Chemistry Ferguson, Michael; University of Alberta Department of Chemistry McDonald, DraftRobert; University of Alberta, Chemistry Rivard, Eric; University of Alberta, Chemistry Is the invited manuscript for consideration in a Special N Burford Issue?: Keyword: Staudinger reaction, phosphazenes, carbene, phosphine https://mc06.manuscriptcentral.com/cjc-pubs Page 1 of 17 Canadian Journal of Chemistry An Unexpected Staudinger Reaction at an N-Heterocyclic § Carbene-carbon Center Matthew M. D. Roy, Linkun Miao, Michael J. Ferguson, Robert McDonald, Eric Rivard* Department of Chemistry, University of Alberta, 11227 Saskatchewan Dr., Edmonton, AB, Canada, T6G 2G2 § This paper is dedicated to Prof. Neil Burford in recognition of his profoundly important scientific and mentorship contributions to the chemical community in Canada. Abstract The previously unreported carbene-phosphine adduct (IPr)PCl2N3, [IPr = (HCNDipp)2C:; Dipp = i Draft 2,6- Pr2C6H3] was synthesized and used as a synthon toward the elusive dichlorophosphazene monomer unit, [Cl2P=N]. (IPr)PCl2N3 was found to undergo halide and azide abstraction when combined with various electrophiles and its thermolysis yielded the unexpected Staudinger reaction product (IPr=N)PCl2. Introduction Originally referred to as ‘inorganic rubber’, poly(dichlorophosphazene) [Cl2P=N]n was first reported by Stokes in 1895.1 This important parent polymer is typically synthesized by the ring- opening polymerization (ROP) of hexachlorophosphazene [Cl2P=N]3, however it was initially of little practical importance due to its propensity to undergo hydrolysis. Later, Allcock and coworkers pioneered the synthesis of well-defined air-stable polyphosphazenes [R2P=N]n via the substitution of main chain chlorine atoms in poly(dichlorophosphazene) with various alkoxides, aryloxides and amides.2 During the search for alternate paths to polyphosphazenes and to gain insight into the ROP mechanism,3 the reactivity of hexachlorophosphazene with Lewis acids4 and Lewis bases5 has been explored. Notably, when reacted with Lewis acids and bases the cyclic nature of [Cl2P=N]3 is generally maintained with the phosphorus centers behaving as electron acceptors and nitrogen atoms as donors. As such, we looked to prepare a dichlorophosphazene monomer [Cl2P=N] through a bottom-up approach that may allow for the 1 https://mc06.manuscriptcentral.com/cjc-pubs Canadian Journal of Chemistry Page 2 of 17 controlled delivery of the [Cl2P=N] unit for materials synthesis; this work gains added inspiration from the selective construction of P-N chains via condensation chemistry6 and the 7 impressive recent isolation of monomeric phosphazenes R2PN via kinetic stabilization. Our group has utilized a donor-acceptor concept to isolate various reactive main group species, typically relying on N-heterocyclic carbenes (NHCs) or N-heterocyclic olefins (NHOs) as ligands.8,9 Perhaps most relevant to the work described in this paper, we have observed that the inorganic acetylene complexes (NHC)HB=NH(LA), (LA = Lewis acid) can be synthesized by thermolysis of carbene-supported azidoboranes (NHC)BH2N3 in the presence of an appropriately bulky Lewis acid.10 We therefore looked to apply a similar dinitrogen extrusion 11 protocol to yield (NHC)Cl2P=N(LA), a masked source of [Cl2P=N]. While we were not successful in preparing the desired species, an interesting NHC-supported phosphine azide 12 i adduct was synthesized, (IPr)PCl2N3 [IPr = (HCNDipp)2C:; Dipp = 2,6- Pr2C6H3], and its subsequent thermal rearrangement to the monomeric iminophosphine (IPr=N)PCl2 was observed. (IPr=N)PCl2 is a potential precursor to Drafta wide range of strongly electron donating ligands of the 13 general form (IPr=N)PR2. The latter transformation, to our knowledge, represents an example of a Staudinger reaction at a carbene-carbon center in preference over a proximal phosphine, and the energetics of this rearrangement were studied computationally. The Lewis basicity of the resulting iminophosphine was demonstrated by the synthesis of the stable phosphine-borane adduct (IPr=N)PCl2•BH3. Results and discussion F With the goal of forming the [Cl2P=N] donor-acceptor species (IPr)Cl2P=N(BAr 3), the n F F soluble azide source [ Bu4N]N3 was first combined with BAr 3 (Ar = 3,5-(CF3)2C6H3) in n F fluorobenzene, leading to the in situ formation of the azidoborate [ Bu4N]N3-BAr 3 after one 11 1 19 1 14 hour [broad B{ H} resonance at -0.6 ppm and a F{ H} resonance at -62.2 ppm in C6D6]. n F 15 [ Bu4N]N3-BAr 3 was then added to the known complex (IPr)PCl3 with the intension of F yielding (IPr)Cl2PN(BAr 3) in a one-pot fashion (via initial Cl/N3 exchange to yield the F 10 1 intermediate (IPr)Cl2PN3(BAr 3) accompanied by the loss of N2 (Scheme 1). The H NMR spectrum of the product mixture after 90 minutes of stirring at room temperature revealed several n + species including the presence of unreacted (IPr)PCl3, a highly soluble [ Bu4N] salt, and a new IPr-containing product. Crystallization of the reaction mixture afforded crystals of the new azidophosphine adduct (IPr)PCl2N3 (1) which was contaminated with ca. 50% of co-crystallized 2 https://mc06.manuscriptcentral.com/cjc-pubs Page 3 of 17 Canadian Journal of Chemistry (IPr)PCl3 (Fig. S4); in the case of 1, substitution of an equatorially-bound chloride by azide transpired, with an overall Tshaped geometry at phosphorus. F Scheme 1. Possible synthetic route to the target species (IPr)Cl2P=N(BAr 3). Draft Scheme 2. Synthesis of (IPr)PCl2N3 (1) and its thermal rearrangement to (IPr=N)PCl2 (2). While this direct approach did not afford the target species (as it did for our reported HB=NH 10 adducts), we looked to prepare (IPr)PCl2N3 (1) in an alternate fashion. As such, when Me3Si- N3 was added to a toluene slurry of (IPr)PCl3 and the mixture stirred for one hour, (IPr)PCl2N3 (1) was obtained as a colorless solid in 94 % yield (Scheme 2) with 1H and 31P{1H} NMR spectra which matched that of the major product formed in the above reaction between (IPr)PCl3 n F and [ Bu4N]N3-BAr 3 (Scheme 2). From this reaction mixture, pure crystals of (IPr)PCl2N3 were obtained and the structure of 1 was determined by single-crystal X-ray crystallography (Fig. 1). 3 https://mc06.manuscriptcentral.com/cjc-pubs Canadian Journal of Chemistry Page 4 of 17 Fig. 1. Molecular structure of (IPr)PCl2N3 (1) with thermal ellipsoids plotted at the 30% probability level. All hydrogen atoms and fluorobenzene solvent have been omitted for clarity. Selected bond lengths [Å] and angles [°]: C1-P 1.8762(15), P-Cl1 2.1950(6), P-Cl2 2.5263(6), P- N3 1.7426(16), N3-N4 1.225(2), N4-N5Draft 1.126(3); Cl1-P-Cl2 179.52(2), Cl1-P-N3 89.57(6), Cl1- P-C1 93.20(5), C1-P-N3 98.34(7). The molecular structure of 1 shows an expected distorted Tshaped geometry, 16 corresponding to an overall AEX4 VSEPR arrangement, indicating the presence of a stereochemically active phosphorus lone pair. One P-Cl bond in 1 is significantly elongated relative to the other [P-Cl(1) = 2.1950(6) Å versus P-Cl(2) = 2.5263(6) Å] and could be a consequence of the strong donor ability of the N-heterocyclic carbene IPr, which in turn lowers the Lewis acidity of the phosphorus atom in 1. Additionally, the CNHC-P distance [1.8762(15) Å] 15 compares well with that of (IPr)PCl3 [1.871(11) Å]. Curious as to whether thermolysis of 1 would yield an NHC-supported phosphinonitrene (R2PN) or dichlorophosphazene oligomers via N2 loss, compound 1 was heated to 80 °C in toluene for one hour (Caution!). As expected, the visible release of a gas from solution was noted and 31P{1H} NMR analysis of the resulting colorless solution revealed the complete disappearance of 1 (δ 6.7 ppm) along with the formation of a new product with a down-field shifted 31P{1H} NMR resonance of 166.4 ppm; the latter 17 resonance is in the range normally seen for monosubstituted phosphorus(III) dihalides RPCl2, suggesting that the expected Staudinger-type oxidation at phosphorus to yield a P(V) species did 4 https://mc06.manuscriptcentral.com/cjc-pubs Page 5 of 17 Canadian Journal of Chemistry not occur.18 However, X-ray analysis of crystals of this product did show that a Staudinger reaction transpired, however via oxidation of the N-heterocyclic carbene ligand (and concomitant 19 loss of N2) to yield the new N-heterocyclic imine-substituted phosphine (IPr=N)PCl2 (2) in an 88 % yield (Scheme 3). Bertrand and coworkers have prepared the backbone-saturated phosphine-imine (SIPr=N)PCl2, [SIPr = (H2CNDipp)2C] by combining the lithiated imide 20 [SIPr=N]Li with PCl3. As an alternative, we have also found that (IPr=N)PCl2 (2) can be synthesized directly from IPr=NSiMe3 and PCl3, with a slightly higher overall yield of 93 % versus the thermal-rearrangement route mentioned above. Draft Fig. 2. Molecular structure of (IPr=N)PCl2 (2) with thermal ellipsoids plotted at the 30% probability level. All hydrogen atoms have been omitted for clarity. Selected bond lengths [Å] and angles [°]: C1-N3 1.319(3), N3-P 1.6023(17), P-Cl1 2.1383(9), P-Cl2 2.1077(8); C1-N3-P 127.64(15), Cl1-P-Cl2 95.01(3), Cl1-P-N3 100.30(7), Cl2-P-N3 101.90(7).
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