The extension of the frustrated Lewis pair (FLP) concept to the transition series with cationic zirconocene-phosphinoaryloxide complexes is demonstrated. Such complexes mimic the reactivity of main group FLPs in reactions such as heterolytic hydrogen cleavage, CO(2) activation, olefin and alkyne addition, and ring-opening of tetrahydrofuran. The interplay between sterics and electronics is shown to have an important role in determining the reactivity of these compounds with hydrogen in particular. The Zr-H species generated from the heterolytic activation of hydrogen is shown to undergo insertion reactions with both CO(2) and CO. Crucially, these transition metal FLPs are markedly more reactive than main group systems in many cases, and in addition to the usual array of reactions they demonstrate unprecedented reactivity in the activation of small molecules. This includes S(N)2 and E2 reactions with alkyl chlorides and fluorides, enolate formation from acetone, and the cleavage of C-O bonds to facilitate S(N)2 type reactions with noncyclic dialkyl ethers.
The cationic zirconocene-phosphinoaryloxide complexes [Cp(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (3) and [Cp*(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (4) were synthesized by the reaction of Cp(2)ZrMe(2) or Cp*(2)ZrMe(2) with 2-(diphenylphosphino)phenol followed by protonation with [2,6-di-tert-butylpyridinium][B(C(6)F(5))(4)]. Compound 3 exhibits a Zr-P bond, whereas the bulkier Cp* derivative 4 was isolated as a chlorobenzene adduct without this Zr-P interaction. These compounds can be described as transition-metal-containing versions of linked frustrated Lewis pairs (FLPs), and treatment of 4 with H(2) under mild conditions cleaved H(2) in a fashion analogous to that for main-group FLPs. Their reactivity in amine borane dehydrogenation also mimics that of main-group FLPs, and they dehydrogenate a range of amine borane adducts. However, in contrast to main-group FLPs, 3 and 4 achieve this transformation in a catalytic rather than stoichiometric sense, with rates superior to those for previous high-valent catalysts.
Using captured waste carbon dioxide
(CCU) as a chemical reagent
is an attractive means to add value to carbon capture and storage
(CCS) and is a high-priority target for manufacturing. One promising
route is to copolymerize carbon dioxide and epoxides, to prepare aliphatic
polycarbonates. In this study, three homogeneous dinuclear Zn and
Mg catalysts, previously reported by our group (see
Kember
M. R.
Knight
P. D.
Reung
P. T. R.
Williams
C. K
Kember
M. R.
Knight
P. D.
Reung
P. T. R.
Williams
C. K
Angew. Chem., Int. Ed.200948931933 and
Kember
M. R.
Williams
C. K.
Kember
M. R.
Williams
C. K.
J. Am. Chem. Soc.20121341567615679) have been investigated using captured and
contaminated carbon dioxide, with cyclohexene oxide, to produce polymers.
Carbon dioxide captured from the carbon capture demonstrator plant
at Ferrybridge Power Station, U.K., is applied for the efficient production
of poly(cyclohexylene carbonate). Remarkably, the dinuclear Zn and
Mg catalysts display nearly equivalent turnover numbers (TON) and
turnover frequencies (TOF) using captured CO2 versus those
using purified CO2. The tolerance of the catalysts to reactions
contaminated with known quantities of exogenous water, nitrogen, SO2, amine, and octadecanethiol are reported. The catalyst activities,
productivities, and selectivities are presented, together with the
polymers’ number-average molecular weights (M
n), dispersities (Đ), and end-group
analyses. The catalysts show high tolerance to protic impurities,
including the addition of amine, thiol, and water. In particular,
under certain conditions, efficient polymerization can be conducted
in the presence of up to 400 equiv of water without compromising catalytic
activity/productivity or selectivity. Furthermore, the catalysts can
selectively produce polycarbonate polyols with molecular weights in
the range of 600−9000 g/mol and disperities <1.10.
Protonation of MeRNH·BH3 (R = Me or H) with HX (X = B(C6F5)4, OTf, or Cl), followed by immediate, spontaneous H2 elimination, yielded the amine-boronium cation salt [MeRNH·BH2(OEt2)][B(C6F5)4] and related polar covalent analogs, MeRNH·BH2X (X = OTf or Cl). These species can be deprotonated to conveniently generate reactive aminoborane monomers MeRN=BH2 which oligomerize or polymerize; in the case of MeNH2·BH3, the two step process gave poly(N-methylaminoborane), [MeNH-BH2]n.
Titanium-phosphorus frustrated Lewis pairs (FLPs) based on titanocene-phosphinoaryloxide complexes have been synthesised. The cationic titanium(IV) complex [Cp(2)TiOC(6)H(4)P((t)Bu)(2)][B(C(6)F(5))(4)] 2 reacts with hydrogen to yield the reduced titanium(III) complex [Cp(2)TiOC(6)H(4)PH((t)Bu)(2)][B(C(6)F(5))(4)] 5. The titanium(III)-phosphorus FLP [Cp(2)TiOC(6)H(4)P((t)Bu)(2)] 6 has been synthesised either by chemical reduction of [Cp(2)Ti(Cl)OC(6)H(4)P((t)Bu)(2)] 1 with [CoCp*(2)] or by reaction of [Cp(2)Ti{N(SiMe(3))(2)}] with 2-C(6)H(4)(OH){P((t)Bu)(2)}. Both 2 and 6 catalyse the dehydrogenation of Me(2)HN·BH(3).
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