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Instruments / Technical Area	Publication Details	Published
I19-Small Molecule Single Crystal Diffraction	Phosphido-bis(borane) complexes of the alkaline earth metals Keith Izod , James M. Watson , Ross W. Harrington , William Clegg Dalton Transactions 50, 1019-1024 DOI: 10.1039/D0DT03895D Diamond Proposal Number(s): [6302] Show Abstract ▼ Abstract: The reaction between two equivalents of {(Me3Si)2CH}(Ph)PH(BH3) (1) and Bu2Mg, followed by two equivalents of BH3·SMe2, gives the corresponding phosphido-bis(borane) complex, which may be crystallised as two distinct chemical species: the complex [{(Me3Si)2CH}(Ph)P(BH3)2]2Mg(THF)4·THF (2a), and two different THF solvates (1 : 1 and 1 : 2) of the solvent-separated ion triples [{(Me3Si)2CH}(Ph)P(BH3)2]2[Mg (THF)6]·THF (2b) and [{(Me3Si)2CH}(Ph)P(BH3)2]2[Mg(THF)6]·2THF (2c). Similar reactions between two equivalents of 1 and either (4-tBuC6H4CH2)2Ca(THF)4 or [(Me3Si)2CH]2Sr(THF)2, followed by two equivalents of BH3·SMe2, give the heavier alkali metal complexes [{(Me3Si)2CH}(Ph)P(BH3)2]2M(THF)4 [M = Ca (3), Sr (4)]. Surprisingly, compounds 2a, 3 and 4 adopt almost identical structures in the solid state, which differ only in the geometrical arrangement of the phosphido-bis(borane) ligands and the hapticity of the borane groups.	Dec 2020
I19-Small Molecule Single Crystal Diffraction	Remote Substituent Effects on the Structures and Stabilities of P═E π-Stabilized Diphosphatetrylenes (R 2 P) 2 E (E = Ge, Sn) Keith Izod , Peter Evans , Paul Waddell , Mike Probert Inorganic Chemistry 55, 10510 - 10522 DOI: 10.1021/acs.inorgchem.6b01566 Diamond Proposal Number(s): [6749] Show Abstract ▼ Abstract: A rare P–E π interaction between the lone pair of a planar P center and the vacant p orbital at the Ge or Sn center provides efficient stabilization for P-substituted tetrylenes (R2P)2E (E = Ge, Sn) and enables isolation of the first example of a compound with a crystallographically authenticated P═Sn bond. Subtle changes in the electronic properties of the bulky aryl substituents in these compounds change the preference for planar versus pyramidal P centers in the solid state; however, variable-temperature NMR spectroscopy indicates that in solution these species are subject to a dynamic equilibrium, which interconverts the planar and pyramidal P centers. Consistent with this, density functional theory studies suggest that there is only a small energy difference between the planar and pyramidal forms of these compounds and reveal a small singlet–triplet energy separation, suggesting potentially interesting reactivities.	Oct 2016
I19-Small Molecule Single Crystal Diffraction	Light-Induced Rearrangement of Thioether-Substituted Phosphanide Ligands: Scope and Limitations of a Remarkable Isomerization Keith Izod , Ewan R Clark , Pamela Foster , Rebecca J. Percival , Ian M. Riddlestone , Ross Harrington , William Clegg Chemistry - A European Journal 19 (19), 6094-6107 DOI: 10.1002/chem.201203918 PMID: 23471708 Diamond Proposal Number(s): [6749] Show Abstract ▼ Abstract: Treatment of the thioether-substituted secondary phosphanes R2PH(C6H4-2-SR1) [R2=(Me3Si)2CH, R1=Me (1PH), iPr (2PH), Ph (3PH); R2=tBu, R1=Me (4PH); R2=Ph, R1=Me (5PH)] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF (1–5Pa) and tmeda (1–5Pb) adducts. Solid-state structures were obtained for the adducts [R2P(C6H4-2-SR1)]Li(L)n [R2=(Me3Si)2CH, R1=nPr, (L)n=tmeda (2Pb); R2=(Me3Si)2CH, R1=Ph, (L)n=tmeda (3Pb); R2=Ph, R1=Me, (L)n=(THF)1.33 (5Pa); R2=Ph, R1=Me, (L)n=([12]crown-4)2 (5Pc)]. Treatment of 1PH with either PhCH2Na or PhCH2K yields the heavier alkali metal complexes [{(Me3Si)2CH}P(C6H4-2-SMe)]M(THF)n [M=Na (1Pd), K (1Pe)]. With the exception of 2Pa and 2Pb, photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R2P(R1)(C6H4-2-S)]M(L)n [M=Li, L=THF (1Sa, 3Sa–5Sa); M=Li, L=tmeda (1Sb, 3Sb–5Sb); M=Na, L=THF (1Sd); M=K, L=THF (1Se)] as the sole products. The compounds 3Sa and 4Sa may be desolvated to give the cyclic oligomers [[{(Me3Si)2CH}P(Ph)(C6H4-2-S)]Li]6 ((3S)6) and [[tBuP(Me)(C6H4-2-S)]Li]8 ((4S)8), respectively. A mechanistic study reveals that the phosphanide–thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2Pa/2Pb, competing intramolecular ?-deprotonation of the n-propyl substituent results in the elimination of propene and the formation of the phosphanide–thiolate dianion [{(Me3Si)2CH}P(C6H4-2-S)]2?.	Mar 2013

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