Celebrating the life of Professor James (Jim) Ralph Hanson.

The reactivity of tin and lead phosphanido complexes with chalogens is reported. The addition of sulfur to [(BDI)MPCy2] (M = Sn, Pb; BDI = CH{(CH3)CN-2,6-iPr2C6H3}2) results in the formation of phosphinodithioates [(BDI)MSP(S)Cy2] regardless of the conditions; however, when selenium is added to [(BDI)MPCy2], a selenium insertion product, phosphinoselenoite [(BDI)MSePCy2], can be isolated. This compound readily reacts with additional selenium to form the phosphinodiselenoate complex [(BDI)MSeP(Se)Cy2]. In contrast, the addition of selenium to [(BDI)SnP(SiMe3)2] results in the formation of the heavy ether [(BDI)SnSeSiMe3]. Differences in the solution and solid-state molecular species of tin phosphinoselenoite and phosphinodiselenoate complexes were probed using multinuclear solution and solid-state NMR spectroscopy.

Three new beta-diketiminatolead(II) chlorides have been synthesised, including [(BDIDmp)PbCl], [(BDIIPP)-PbCl] and [(BDIph)PbCl] (BDIDMP = [N{(2,6-Me2C6H3)C(Me)}(2)CH], BDIIPP = [N{(4-(PrC6H4C)-Pr-i(Me)}(2)CH] and BDIPh = [N{(C6H5)C(Me)}(2)CH]). Addition of sodium or potassium-alkoxide salts to [(BDIIPP)PbCl] or [(BDIPh)PbCl] resulted in the unexpected formation of bis(beta-diketiminato)lead(II) complexes, [(BDIIPP)(2)Pb] and [(BDIPh)(2)Pb], whereas addition to [(BDIDMP)PbCl] led to the expected lead alkoxo complex, [(BDIDMP)-(PbOBu)-Bu-t] The lead(II) triflate complex, [(BDIDMP)PbOTf], was synthesised by treatment of [(BDIDMP)PbCl] with AgOTf. (C) 2014 Elsevier Ltd. All rights reserved.

Meeting Summary The 22nd annual symposium of the International Isotope Society's United Kingdom Group took place at the Møller Centre, Churchill College, Cambridge, UK, on Friday, 18 October 2013. The meeting was attended by 65 delegates from academia and industry; the life sciences; and chemical, radiochemical and scientific instrument suppliers. Delegates were welcomed by Dr Ken Lawrie (GlaxoSmithKline, UK, chair of the IIS UK group). The subsequent scientific programme consisted of oral and poster presentations on isotopic chemistry and applications of labelled compounds, or of chemistry with potential implications for isotopic synthesis. Both short-lived and long-lived isotopes were represented, as were stable isotopes. The symposium programme was divided into a morning session chaired by Dr Karl Cable (GlaxoSmithKline, UK) and afternoon sessions chaired by Mr Mike Chappelle (Quotient Biosciences, UK) and by Dr Nick Bushby (AstraZeneca, UK). The UK meeting concluded with remarks from Dr Ken Lawrie (GlaxoSmithKline, UK).

The structure of a triclinic form of the organolithium derivative LiR, R = C(SiMe3)2(SiMe2{hpp}) (1) (hppH = 1,3,4,6,7,8,-hexahydro-2H-pyrimido[1,2-a]pyrimidine) comprises dimers [1]2 held together by Li···H3C interactions like those in the polymeric structure [1]∞ of the previously described orthorhombic form. Compound 1 reacts with the chlorides MCl2 (M = Hg or Sn) to give compounds HgRCl (2) or SnRCl (3), which have been characterised by NMR spectroscopy and X-ray crystallography. The structural parameters and conformations of the metallacycles MRLn are compared with those in related compounds containing bulky organosilicon ligands with pendant nitrogen donors. Compound 3 reacts with Li[P{H}Ar*] (Ar* = 2,4,6-tBu3C6H2) to give the crowded phosphanide SnR(P{H}Ar*) (4).

Addition of one equivalent of selenium to a germanium-phosphanide complex results in insertion of selenium into the Ge-P bond, not oxidation at germanium or phosphorus. Addition of excess selenium results in oxidation at phosphorus, although of germanium oxidation is still observed.

A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR(2)) (M = Ge, Sn, Pb; BDI = CH{(CH(3))CN-2,6-iPr(2)C(6)H(3)}(2); R = Ph, Cy, SiMe(3)) have been synthesized. Two different conformations (endo and exo) are observed in the solid-state; the complexes with an endo conformation have a planar coordination geometry at phosphorus (M = Ge, Sn; R = SiMe(3)) whereas the complexes possessing an exo conformation have a pyramidal geometry at phosphorus. Solution-state NMR studies reveal through-space scalar coupling between the tin and the isopropyl groups on the N-aryl moiety of the BDI ligand, with endo and exo exhibiting different J(SnC) values. The magnitudes of the tin-phosphorus and lead-phosphorus coupling constants, |J(SnP)| and |J(PbP)|, differ significantly depending upon the hybridization of the phosphorus atom. For Sn(BDI)(P{SiMe(3)}(2)), |J(SnP)| is the largest reported in the literature, surpassing values attributed to compounds with tin-phosphorus multiple-bonds. Low temperature NMR studies of Pb(BDI)(P{SiMe(3)}(2)) show two species with vastly different |J(PbP)| values, interpreted as belonging to the endo and exo conformations, with sp(2)- and sp(3)-hybridized phosphorus, respectively.

Angewandte ChemieVolume 121, Issue 36 p. 6721-6723 Highlight Metallorganische Verbindungen der schwereren s-Block-Elemente – was kommt als Nächstes? J. David Smith Dr., J. David Smith Dr. [email protected] Department of Chemistry, School of Life Sciences, University of Sussex (Großbritannien), Fax: (+44) 1273-876-687Search for more papers by this author J. David Smith Dr., J. David Smith Dr. [email protected] Department of Chemistry, School of Life Sciences, University of Sussex (Großbritannien), Fax: (+44) 1273-876-687Search for more papers by this author First published: 19 August 2009 https://doi.org/10.1002/ange.200901506Citations: 10Read the full textAboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Schwergewichte: Ein neuartiges Dicaesiummethandiid und eine metallorganische Verbindung von CaI ohne Ca-Ca-Bindung (siehe Bild) sind Beispiele für Spezies, in denen Metalle an Anionen koordinieren. 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The alkylpotassium compound KC{SiMe(3)}(2){SiMe(2)hpp} (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) reacts with a slurry of CaI(2) in toluene to give the internally coordinated dialkylcalcium(II) complex Ca(C{SiMe(3)}(2){SiMe(2)hpp})(2). The molecular structure in the solid state shows short Ca-N and long Ca-C bonds and a wide C-Ca-C angle. The (1)H and (13)C NMR spectra suggest that the metallacycle is transiently opened in toluene at room temperature.

Single-crystal X-ray diffraction of MC(SiMe3)(2)(SiMe(2)hpp) (M = Li, K; hppH = 1,3,4,6,7,8,-hexahydro-2H-pyrimido[1,2-a]pyrimidine) showed nonsolvated organometallic compounds in which the iminonitrogen of the guanidine forms strong intramolecular bonds to generate six-membered metallacycles.

The alkylcobalt halide [{(2-C5H4N)Me2Si (Me3Si)(2)CCoCl](2) (2) and the lithium silanolatocobaltates Li(THF)(2)(mu-Br)(2)Co(mu-OSiMe3)(2)Co(mu-Br)(2)Li(THF)(2) (4) and [LiBr{Li(THF)}(2) {CoBr(OSiMe3)(3)}](2) (5) form centrosymmetrical halogen-bridged dimers in the crystalline state. Compound 4 shows bromide bridges between lithium and cobalt, and silanolato bridges between the cobalt atoms. Below 200 K there are significant antiferromagnetic interactions between the cobalt centres. Compound 5 crystallises in a novel structure in which two cubane-like fragments containing silanolato bridges are linked together through a Li2Br2 ring. (C) 2004 Elsevier B.V. All rights reserved.

The lithium derivative Li(THF)C(SiMe3)(2)(SiMe2C5H4N-2) (1) reacted with AlCl3 or Me2AlCl to give, respectively, the monomeric compounds AlCl2C(SiMe3)(2)(SiMe2C5H4N-2) (2a) and AlMe2C(SiMe3)(2)(SiMe2C5H4N-2) (2b). The product from reaction with commercially available GaBr3 was the analytically pure monomeric heterocycle GaBr(OH)C(SiMe3)(2)(SiMe2C5H4N-2) (3), indicating that the starting halide had been partially hydrolysed before use. The reaction between I and commercially available InCl3 gave a homogenous white solid [InCl(mu-X)C(SiMe3)(2)(SiMe2C5H4N-2)](2) (4) with X = Cl (59%) or OH (41%). The X-ray crystal structures of 2a. 3, and 4 have been determined. (C) 2004 Elsevier B.V. All rights reserved.

The oxygen-bridged, silicon-substituted alkane {(Me3Si)(2)CH(SiMe2)}(2)O (1) may be prepared by the reaction of {(Me3Si)(2)CH}Li with ClSiMe2OSiMe2Cl in refluxing THF. Similarly, the alkane {(Me3Si)(Me2MeOSi)CH(SiMe2CH2)}(2) (2) is readily accessible from the reaction between {(Me3Si)(Me2MeOSi)CH}Li and ClSiMe2CH2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the polymeric complex [[{(Me3Si)(2)C(SiMe2)}(2)O]K-2(OEt2)](infinity)[5(OEt2)] after recrystallisation. Treatment of 2 with two equivalents of either MeLi or MeK gives the corresponding complexes [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}(2)Li][Li(DME)(3)][7(DME)(3)] and [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}(2)K-2](n) (8), respectively, after recrystallisation. Treatment of the alkane (Me3Si)(2)(Me2MeOSi)CH with one equivalent of MeK gives the polymeric complex [{(Me3Si)(2)(Me2MeOSi)C}K](infinity) (3). These compounds have been identified by H-1 and C-13{H-1} NMR spectroscopy and elemental analyses and compounds 5(OEt2), 7(DME)3 and 3 have been further characterised by X-ray crystallography. Compound 7(DME)3 crystallises as a solvent-separated ion pair, whereas 5(OEt2) and 3 adopt polymeric structures in the solid state.

Silicone waxes, sealants, and post-it slips are present in every home in the developed world. Millions of tonnes of silicones are manufactured each year. Conferences on organosilicon chemistry and European Silicon Days are part of the chemistry scene. Yet in 1960, Colin Eaborn, who has died aged 80, was able to write a 500-page book entitled Organosilicon Compounds1 and cover all aspects of the subject as it was then known. Organosilicon chemistry developed so much during Eaborn’s research career that it would be simply impossible for one person to undertake such a task today. Eaborn was born in Cheshire (UK) in 1923 and completed his BSc degree in 1944 and PhD in 1947 at the University of Wales, Bangor. His research supervisor was the physical organic chemist E. D. Hughes, who gave him the task (which he thought would take a couple of years) of demonstrating the existence of the SN1, SN2, E1, and E2 mechanisms for reactions at silicon centers analogous to those recently discovered for reactions at carbon centers. This was a wholly unrealistic assignment, but it got Eaborn started on extraordinarily fruitful research on organosilicon compounds, electrophilic aromatic substitution (one of his first papers was on the cleavage of the aryl–silicon bond in p-MeOC6H4SiMe3), and the use of bulky groups to stabilize species that would otherwise be too reactive to study.2 He collaborated extensively with colleagues both in his own department and, more informally, throughout the world, and covered an astonishing range of topics in more than 550 research publications. Many of these topics were developed further as his co-workers became independent. Work with David Walton on poly(alkynyl)trimethylsilanes led to investigations on molecules in space and was one of the factors that prompted Nobel Laureate Harry Kroto to look for C60. Work with Roger Taylor on aromatic compounds led to a huge volume of further work also extended to cover fullerenes. Work with Richard Jackson, Andrew Hudson, and Iain Davidson led to extensive studies of radicals both in solution and in the gas phase. Work with Joseph Chatt and Alan Pidcock on compounds of Group 14 elements as ligands in transition-metal chemistry was followed by an extensive collaboration with David Smith resulting in over 100 publications on tris(trimethylsilyl)methyl (trisyl) and related compounds covering every group of the periodic table except the noble gases.3 There were also significant collaborations with colleagues in Germany, Poland, Italy, and New Zealand. Eaborn’s first appointment in 1947 was at University College Leicester (now the University of Leicester). He left there in 1961 to become the first professor of chemistry at the then new University of Sussex. As Head of Department, Dean, and Pro-Vice-Chancellor, Eaborn quickly built up a vibrant and internationally recognized research school, attracting other eminent chemists as colleagues, including six Fellows of the Royal Society and three Nobel Prize winners. He persuaded inorganic, organic, and physical chemists to talk to each other rather than compete for resources and urged his colleagues to make daring innovations in university teaching. The most notable of these new methods was the so-called “degree by thesis”, in which a thesis and an oral presentation replaced the traditional written examinations of undergraduates in the UK. This initiative attracted original and highly motivated students, but it had to be phased out because of the legal implications of allowing technically unqualified undergraduates to work in research laboratories. Eaborn received numerous honors and prizes. He was elected to the Fellowship of the Royal Society in 1970. He received the Frederick Stanley Kipping Award of the American Chemical Society in 1964: the first non-American to receive this prestigious prize. He received the Organometallic Award of the Royal Society of Chemistry in 1974, its Ingold Medal in 1976, and the Main Group Award in 1988. Although he was not a highly visible public figure, he had considerable influence on the development of chemistry at university level in the second half of the twentieth century. He chaired a committee (1966-1970) on the relationship between chemistry courses and the needs of industry, was honorary secretary of the Chemical Society (now the Royal Society of Chemistry) from 1965 to 1970, and served on the Council of the Royal Society from 1978 to 1980 and 1988 to 1989. He was instrumental in setting up regular meetings of the heads of chemistry departments to consider matters of mutual interest, and he corresponded with hundreds of chemists, especially in Europe, as a founding editor of the Journal of Organometallic Chemistry. Many are grateful for the care he gave to presentation, clarity, and good English in the manuscripts he received. He was the UK representative on the British–Italian Mixed Cultural Commission. Colin Eaborn is survived by his wife Joyce, who provided support and companionship for more than 50 years. He leaves numerous students, co-workers, and colleagues who have been encouraged by his enthusiasm and generosity and cheered by his sense of humor.

Metallation of (HMe2Si)(Me3Si)(2)CH (1) by LiMe gave the organolithium compound Li(THF)(2)C(SiMe3)(2)(SiMe2H) (2a), which exists in toluene solution as a mixture of covalent species and ion pairs [Li(THF)(4)][Li{C(SiMe3)(2)(SiMe2H)}(2)] (2b). Treatment of a mixture of 1 and LiMe with KOBu1 gave KC(SiMe3)(2)(SiMe2H) (3). This reacted with AlMe2Cl in hexane/THF to give Al(THF)Me-2{C(SiMe3)(2)(SiMe2H)} (4). Treatment of (HMe2Si)(PhMe2Si)(2)CH (5) with LiMe in Et2O/THF gave the THF adduct [Li(THF)(2)C(SiMe2Ph)(2)(SiMe2H)] (6); in the presence of KOBut the solvent-free [K][C(SiMe2Ph)(2)(SiMe2H)] (7) was obtained. Crystal structure determinations showed that 6 crystallizes in a molecular lattice and 7 in an ionic lattice in which the coordination sphere of the potassium comprises phenyl groups and hydrogen atoms attached to silicon, as well as the central carbon of the bulky carbanion. Compound 7 reacted with an excess of AlMe2Cl to give [AlClMe{C(SiMe2Ph)(2)(SiMeH)}](2) (8) and AlMe3. A small amount of the methoxo derivative [Al(OMe)Me{C(SiMe2Ph)(2)(SiMe2H)}](2) (9) was obtained as a byproduct, presumably after the accidental admission of traces of air. X-ray structural determinations showed that 8 forms halogen-bridged dimers, with the bulky ligands in the anti-configuration, and 9 forms methoxo-bridged species in which the bulky ligands are syn. (C) 2004 Elsevier B.V. All rights reserved.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The lithium reagent Li(THF)(2) {C(SiMe3)(2)(SiMe2NMe2)} (3) reacts with a molar equivalent of anhydrous zinc bromide to give the dimeric compound [Zn(mu-Br){C(SiMe3)(2)(SiMe2NMe2)}](2) (2a), in which zinc is four-coordinate. The product from a similar reaction with Li{C(SiMe3)(2)(SiMe2NPhMe)} is the lithium zincate [Li(THF)(2)(mu-Br)(2)Zn {C(SiMe3)(2)(SiMe2NPhMe)}] (4), in which the zinc is only three-coordinate. The crystal structures of 2a and 4 have been determined. (C) 2004 Elsevier B.V. All rights reserved.

By reaction of Me3SiSBu with anhydrous tin(II) chloride bis(butylthio)tin was obtained that exemplified a coordination polymer [Sn(SBu)2] n , whose elementary unit contained according to X-ray diffraction study three independent four-membered rings Sn2S2 of unusual geometry. It was demonstrated that polymeric thiolates [E(SBu)2] n (E = Ge, Sn) readily reacted with TsiLi (Tsi = C(SiMe3)3) in a mixed solvent ether THF affording in a good yield ate-complexes [(Me3Si)3CE(μ-SBu)2Li(THF)2]. Both complexes contain a four-membered ring in a butterfly conformation where the lithium atom is symmetrically bonded to both sulfur atoms, and the coordination polyhedra of Ge and Sn atoms may be regarded as distorted tetrahedra AB3X, where one of coordination places is occupied by unshared electron pair. The structure of the ate-complexes observed in a crystal is conserved also in solution of nonpolar solvents.

The first structurally characterized dialkylaluminate [{Li(THF)}(AltBu{C(SiMe3)(3)}H-2)](2) (3) is dimeric in the solid state with [Li(THF)](+) and [AltBu{C(SiMe3)(3)}H-2](-) fragments linked by (LiH)-H-...-Al bridges.