“…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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“…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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“…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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“…The (31)P NMR data for [Th(PH(2))(Tren(TIPS))] (1, Tren(TIPS) = {N(CH(2)CH(2)NSiPr(i)(3))(3)}(3–)), [Th(PH)(Tren(TIPS))][Na(12C4)(2)] (2, 12C4 = 12-crown-4 ether), [{Th(Tren(TIPS))}(2)(μ-PH)] (3), and [{Th(Tren(TIPS))}(2)(μ-P)][Na(12C4)(2)] (4) demonstrate a chemical shift anisotropy (CSA) ordering of (μ-P)(3–) > (=PH)(2–) > (μ-PH)(2–) > (−PH(2))(1–) and for 4 the largest CSA for any bridging phosphido unit. …”
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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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“…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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