“…Reaction of [U(Tren(TIPS))(PH(2))] (1, Tren(TIPS)=N(CH(2)CH(2)NSiPr(i) (3))(3)) with C(6)H(5)CH(2)K and [U(Tren(TIPS))(THF)][BPh(4)] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren(TIPS))}(2)(μ‐PH)] (3). …”
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“…Catalytic reduction of N(2) to NH(3) by a Ti complex has been achieved, thus now adding an early d‐block metal to the small group of mid‐ and late‐d‐block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH(3) by N(2) reduction and protonolysis under homogeneous, abiological conditions. Reduction of [Ti(IV)(Tren(TMS))X] (X=Cl, 1A; I, 1B; Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3)) with KC(8) affords [Ti(III)(Tren(TMS))] (2). …”
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“…We report that reduction of [Th(Tren(TIPS))(OCP)] (2, Tren(TIPS)=[N(CH(2)CH(2)NSiPr(i) (3))](3−)), with RbC(8) via [2+2+1] cycloaddition, produces an unprecedented hexathorium complex [{Th(Tren(TIPS))}(6)(μ‐OC(2)P(3))(2)(μ‐OC(2)P(3)H)(2)Rb(4)] (5) featuring four five‐membered [C(2)P(3)] phosphorus heterocycles, which can be converted to a rare oxo complex [{Th(Tren(TIPS))(μ‐ORb)}(2)] (6) and the known cyclometallated complex [Th{N(CH(2)CH(2)NSiPr(i) (3))(2)(CH(2)CH(2)SiPr(i) (2)CHMeCH(2))}] (4) by thermolysis; thereby, providing an unprecedented example of reductive cycloaddition reactivity in the chemistry of 2‐phosphaethynolate. …”
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“…We report the direct synthesis of the terminal pnictidenes [An(Tren(TCHS))(PnH)][M(2,2,2‐cryptand)] (Tren(TCHS)={N(CH(2)CH(2)NSiCy(3))(3)}(3−); An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(Tren(TCHS))(PnH(2))] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). …”
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“…We report that treatment of [M(Tren(DMBS))(I)] (M = U, 1; Th, 2; Tren(DMBS) = {N(CH(2)CH(2)NSiMe(2)Bu(t))(3)}(3–)) with NaN(3) or KN(3), respectively, affords very rare examples of actinide molecular square and triangle complexes [{M(Tren(DMBS))(μ-N(3))}(n)] (M = U, n = 4, 3; Th, n = 3, 4). …”
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“…Treatment of [U(IV)(N(3))(Tren(TIPS))] (1, Tren(TIPS) = {N(CH(2)CH(2)NSiPr(i)(3))(3)}(3−)) with excess Li resulted in the isolation of [{U(IV)(μ-NLi(2))(Tren(TIPS))}(2)] (2), which exhibits a diuranium(iv) ‘diamond-core’ dinitride motif. …”
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“…We report the synthesis and characterisation of a family of diuranium(iv)-μ-chalcogenide complexes including a detailed examination of their electronic structures and magnetic behaviours. Treatment of [U(Tren(TIPS))] [1, Tren(TIPS) = N(CH(2)CH(2)NSiPr(i) (3))(3)] with Ph(3)PS, selenium or tellurium affords the diuranium(iv)-sulfide, selenide, and telluride complexes [{U(Tren(TIPS))}(2)(μ-E)] (E = S, 2; Se, 5; Te, 6). …”
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“…The reaction of [Zr(Tren(DMBS))(Cl)] [Zr1; Tren(DMBS)=N(CH(2)CH(2)NSiMe(2)Bu(t))(3)] with NaPH(2) gave the terminal parent phosphanide complex [Zr(Tren(DMBS))(PH(2))] [Zr2; Zr−P=2.690(2) Å]. …”
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“…The synthesis and characterisation is presented of the compounds [An(Tren(DMBS)){Pn(SiMe(3))(2)}] and [An(Tren(TIPS)){Pn(SiMe(3))(2)}] [Tren(DMBS)=N(CH(2)CH(2)NSiMe(2)Bu(t))(3), An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; Tren(TIPS)=N(CH(2)CH(2)NSiPr(i) (3))(3), An=U, Pn=P, As, Sb; An=Th, Pn=P, As, Sb]. …”
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“…After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(Tren(TIPS))}(2)(μ‐η(2):η(2)‐As(2)H(2))] (3, Tren(TIPS)=N(CH(2)CH(2)NSiPr(i) (3))(3); Pr(i)=CH(CH(3))(2)). …”
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