A simple, one-step procedure for the formation of chiral metallamacrocycles.
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Chelating Agents↗
Biomedical subjects
Michael J Ferguson
Publications and source records attributed to Michael J Ferguson.
Donor-rich and acceptor-rich pyridine-phosphadiazonium adducts: diversifying the Lewis acceptor chemistry of phosphorus(III).
[Mes*NP(DMAP)2][OTf] represents the first ligand-rich coordination complex of a phosphorus(III) Lewis acceptor, and a three coordinate hypervalent electron-rich (lone pair bearing) center; further diversification is demonstrated by, [(Mes*NP)2(4,4'-BIPY)][OTf]2, representing an acceptor-rich dication.
Journal Article↗
Structurally diverse Rh(I) and Mn(I) complexes derived from the new ambidentate indene ligand, (1-[iPr2P(S)]-2-[NMe2])C9H6.
A new indene-based ligand featuring pendant phosphine sulfide and amine donor fragments has been developed; Rh(I) coordinates to the neutral form of the ligand in a kappa2-[N,S] fashion, while the anionic form of the ligand binds Rh(I) and Mn(I) in kappa2-[C,S] and eta5 modes, respectively.
Crystallography, X-Ray↗
Synthesis and structures of complexes demonstrating the coordinative versatility of the 2,4-diimino-3-phosphinopentene anion (gamma-phosphino-beta-diketiminate).
The synthesis and characterization of a 2,4-diimino-3-phosphinopentene anion (gamma-phosphino-beta-diketiminate) is reported and enables diversification of the beta-diketiminate ligand framework, which has been widely employed across the periodic table. Phosphines are observed to adopt the gamma-position of the ligand rather than the N,N' chelate. While aluminum and lithium adopt the familiar N,N' chelate arrangement with the new 2,4-diimino-3-phosphinopentene anion ligand, reactions with AsCl(3) or SbCl(3) result in substitution at the beta-methyl position on the ligand backbone, realizing novel P-->E (E = As or Sb) intramolecular coordination. The chemistry of the 2,4-diimino-3-phosphinopentene anion can be monitored by the (31)P NMR chemical shifts, which are distinctively diagnostic of the coordinative engagement of the ligand.
Journal Article↗
Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond formation.
A series of phosphine-diphenylphosphenium donor-acceptor cationic complexes have been synthesized and comprehensively characterized (phosphine = diphenylchlorophosphine, triphenylphosphine, trimethylphosphine, and tricyclohexylphosphine). The complexes involve homoatomic P-P coordinate bonds that are susceptible to ligand exchange reactions highlighting a versatile new synthetic method for P-P bond formation. Phosphenium complexes of 1,2-bis(diphenylphosphino)benzene and 1,2-bis(tert-butylphosphino)benzene undergo unusual rearrangements to give a "segregated" diphosphine-phosphonium cation and a cyclic di(phosphino)phosphonium cation, respectively. The rearrangement products reveal the kinetic stability of the phosphine-phosphenium bonding arrangement.
Journal Article↗
Preparation and structure of 2-iodoxybenzoate esters: soluble and stable periodinane oxidizing reagents.
Esters of 2-iodoxybenzoic acid (IBX-esters) are potentially valuable oxidizing reagents belonging to a new class of pentavalent iodine compounds with a pseudo benziodoxole structure.
Esters↗
Homoatomic P --> P coordination: a versatile synthetic approach to polyphosphorus dications.
Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems.
Journal Article↗
IBX amides: a new family of hypervalent iodine reagents.
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Alcohols↗
A ruthenium catalyst that does not require an N-H ligand to achieve high enantioselectivity for hydrogenation of an alkyl-aryl ketone.
Ruthenium catalysts of the form trans-RuCl2((R)-(S)-Josiphos)L2 where L2 = pyridine or 1,2-diamine, have been synthesized that display high catalytic activity towards the hydrogenation of 1'-acetonaphthone.
Journal Article↗
Coordination-driven self-assembly: solids with bidirectional porosity.
Coordination-driven self-assembly reactions have been used in the preparation of a variety of discrete supramolecular species, some of which have shown promise as synthetic receptors. Many highly ordered coordination polymers and porous networks have been prepared in a similar fashion. While a few of these solids are capable of the uptake of small organic molecules in the resultant molecular channels, the formation of truly porous structures has frequently been thwarted by lattice interpenetration. A strategy for the formation of porous solids that may circumvent this problem is based on the covalent construction of nanoscale macrocycles which, when eclipsed in the solid state, may lead to porous, tubular assemblies. We have incorporated these concepts toward the realization of a bidirectionally porous solid. The metal-directed, self-assembly of a conjugated, macrocyclic ligand provides a discrete, supramolecular entity in solution and the solid state. X-ray crystallographic analysis establishes that this assembly packs such that bidirectional channels are realized, and the incorporation of only ClCH2CH2Cl into the crystal lattice demonstrates that these channels are potentially suitable for the selective uptake of small organic guests.
Crystallography, X-Ray↗
Intercalation of alcohols in Ag sulfonates: topotactic behavior despite flexible layers.
This article presents the inaugural intercalation study of a layered metal sulfonate network. Silver triflate forms intercalation complexes with straight chain primary alcohols from ethanol (C(2)H(5)OH) to eicosanol (C(20)H(41)OH). Single-crystal data for the EtOH adduct, 1, are presented which show that the intercalation is coordinative to Ag. In contrast to many other layered hosts, no preheating of Ag triflate is required to liberate a coordination site for intercalation to take place, owing to the ability of the triflate ion to reorient. Crystal structure parameters for 1: C(4)H(6)F(6)S(2)O(7)Ag(2), a = 5.345(7) A, b = 11.310(2) A, c = 12.004(2) A, alpha = 116.87(1) degrees, beta = 90.46(1) degrees, gamma = 99.59(1) degrees, triclinic, space group P, Z = 2. Intercalate 1 presents the triflate ion in an unprecedented mu(5)-coordination mode. PXRD data on the family of complexes show that the intercalation is topotactic, as verified by the linear increase in d-spacing and calculated c-axis lengths for the intercalates, with increasing chain length. The data also show that the alcohol intercalates adopt an interdigitated rather than bilayer arrangement.
Journal Article↗