Bryan M. Gatehouse

Bio: Bryan M. Gatehouse is an academic researcher from Monash University, Clayton campus. The author has contributed to research in topics: Crystal structure & Denticity. The author has an hindex of 21, co-authored 92 publications receiving 1346 citations.

Organoamidometallics. I. Syntheses of [N,N′-Bis(Polyfluorophenyl)Ethane-1,2-Diaminato(2-)]Platinum(II) Complexes by Decarboxylation

Abstract: Reaction of PtCl2(en) (en = ethane-1,2-diamine) with thallous pentafluorobenzoate in hot pyridine ( py ) or 4-methylpyridine ( mepy ) yields the [N,N′- bis (2,3,5,6-tetrafluorophenyl)ethane-1,2-diaminato(2-)]platinum(II) complexes, Pt[N(p-HC6F4)CH2]2( py )2 (1a) and Pt[N(p- HC6F4)CH2]2( mepy )2 (1b). The route to (1a) is considered to involve formation of [Pt(en)( py )2](O2CC6F5)2 (2), decarboxylation of (2) into Pt(NHCH2)2( py )2 (1c) and pentafluorobenzene, and nucleophilic attack of (1c) on C6F5H. Complex (1a) has also been prepared by decarboxylation of (2), reaction of PtI2(en) and TlO2CC6F5, and reaction of PtCl2(en), C6F5H, and TlO2CC6F4H-p in boiling pyridine. From reaction of PtCl2(en), TlO2CC6F4H-p, and the appropriate polyfluorobenzene (RF) in boiling pyridine or 4-methylpyridine, the organoamidoplatinum compounds Pt(NRCH2)2L2(R = C6F5, p-MeC6F4, p-ClC6F4, p-BrC6F4, p-IC6F4, 2,3,5-F3C6H2, or p-C6F5C6F4, L = py and R = C6F5, L = mepy ) have been prepared. Analogous reactions of PtCl2( pn )( pn = propane-1,3-diamine) give the complexes Pt[NR(CH2)3NR]( py )2 (R = C6F5 or p-HC6F4). Spectroscopic evidence for the structures is discussed. The polyfluorophenyl groups confer stability to water on ethane-1,2-diaminato(2-)platinum(II) complexes, and this is attributable to delocalization of non-bonded lone pairs from the amido nitrogens into the polyfluorophenyl rings.

Crystal and molecular structure of an octahedral iron(III) complex with a sulphur-containing Schiff-base ligand: bis(2-aminoethylthiosalicylideneiminato)iron(III) chloride

Abstract: The crystal and molecular structure of the title compound (1) has been determined from diffractometer data by three-dimensional Patterson and Fourier methods and refined by block-diagonal least-squares to R 0·077 for 1302 independent non-zero reflections. Crystals are monoclinic, space group P2l/c, with a= 8·75(1), b= 21·92(2), c= 11·07(1)A, β= 114·0(2)°, and Z= 4. The iron atom is octahedrally co-ordinated by two terdentate Schiff-base ligands, with Fe–S(1) 2·21 (1), Fe–N(1)(amine) 2·08(3), Fe–N(2)(imine) 1·93(2)A; Fe⋯Cl– is 4·51 (1)A.

Crystal and molecular stucture of (NN-dimethylbenzylamine-2C,N)(N-phenylsalicylaldiminato)palladium(II)

Abstract: The title compound crystallizes in the monoclinic space group P21, with a= 8·629(5), b= 10·755(8), c= 11·116(9)A, β= 107·2(1)°, and Z= 2. The structure has been determined from diffractometer data by Patterson and Fourier methods and refined to R 0·048 for 1967 independent non-zero reflections. The crystals are built up of discrete molecules, the palladium atom having approximate square planar geometry, with the two nitrogen atoms mutually trans. Bond distances are : Pd–O 2·094, Pd–N(1)(imine) 2·037, Pd–N(2)(amine) 2·090, and Pd–C(16) 1·981 A.

Interaction of methylmercury(II) with bidentate ligands containing pyridine and pyrazole rings. Synthesis and structure of methyl[1‐(2‐pyridyl)pyrazole]mercury(II) nitrate and [di(1‐pyrazolyl)methane]methylmercury(II) nitrate

Abstract: The complexes [MeHgL]N03[L = 1-(2-pyridyl)pyrazole or di(1-pyrazolyl)methane] have L present as bidentate ligands to give irregular three coordination for Hg in the CHgN2 moieties. The 1-(2-pyridyl)pyrazole complex has C(1)-Hg-N(1) 168(2)° and Hg-N(1) 2·21(3) A [N(1) is the pyrazole donor atom], Hg-N(1')(pyridine ring) 2·61(5) A, and nitrate oxygen atoms 2·97(3), 3·07(3), and 3·14(3) Afrom Hg. The di(l-pyrazolyl)methane cation complex has C(1)-Hg-N(1) 179(1), Hg-N(1) 2·16(1), Hg-N(1') 2·96(2) A, and nitrate oxygen atoms 2·88(2)and 2·90(2) A from Hg. In both structures the cations and anions are grouped to form [MeHgL]NO3 dimeric units via Hg...O interactions.

Palladium-catalyzed cross-coupling reactions in total synthesis.

Abstract: In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Cascade reactions in total synthesis.

Abstract: The design and implementation of cascade reactions is a challenging facet of organic chemistry, yet one that can impart striking novelty, elegance, and efficiency to synthetic strategies. The application of cascade reactions to natural products synthesis represents a particularly demanding task, but the results can be both stunning and instructive. This Review highlights selected examples of cascade reactions in total synthesis, with particular emphasis on recent applications therein. The examples discussed herein illustrate the power of these processes in the construction of complex molecules and underscore their future potential in chemical synthesis.

The Diels--Alder reaction in total synthesis.

Abstract: The Diels-Alder reaction has both enabled and shaped the art and science of total synthesis over the last few decades to an extent which, arguably, has yet to be eclipsed by any other transformation in the current synthetic repertoire. With myriad applications of this magnificent pericyclic reaction, often as a crucial element in elegant and programmed cascade sequences facilitating complex molecule construction, the Diels-Alder cycloaddition has afforded numerous and unparalleled solutions to a diverse range of synthetic puzzles provided by nature in the form of natural products. In celebration of the 100th anniversary of Alder's birth, selected examples of the awesome power of the reaction he helped to discover are discussed in this review in the context of total synthesis to illustrate its overall versatility and underscore its vast potential which has yet to be fully realized.