Manuel Aquino
B.A. 1983 Queen's University
B.Sc. 1985 Queen's University
M.Sc. 1987 Queen's University
Ph.D. 1991 Carleton University (Dinuclear Pentaammineruthenium Complexes)
Post Doctorate: 1991-1993 University of Newcastle/King's College, UK - NATO Science Postdoctoral Fellow (group of Dr. A. Geoffrey Sykes, Bio-inorganic chemistry of the iron enzymes purple acid phosphatase (PAP) and ribonucleotide reductase (RNR))
Research in our lab involves the synthesis, characterization and study of various, particularly mixed-valent, dimetal tetracarboxylates, M2(O2CR)4L2, where M has primarily been ruthenium (Ru), osmium (Os), rhodium (Rh) and copper (Cu) but now extends to rhenium (Re) as well. These complexes are highly flexible “building blocks” which can be modified and linked together in various ways to generate such things as molecular magnetic and electronic devices (such as quantum-dot cellular automata), liquid crystals (metallomesogens) with novel properties, inorganic drugs for cancer treatment, and catalysts.
The mixed-valent diruthenium complexes can also be “disassembled” into mononuclear Ru(II) and Ru(III) complexes that are difficult to synthesize via conventional routes. This methodology is being further developed in our lab for very useful “chiral induction” reactions where "disassembly" takes place with chiral (R or S) phosphines leading to specific optical isomers (D or L) of octahedral ruthenium complexes in very high enantiomeric excess.
Journal Articles Submitted or in Preparation
63. Meshari M. Aljohani, Katherine N. Roberston, and Manuel A.S. Aquino, "Disassembly of Diruthenium(II,III) Tetraacetate with Unsaturated Diphosphine Ligands", J. Coord. Chem., manuscript in preparation.
Refereed Journal Articles
62. Anthony J. Aquino, Daniel Gerrior, T. Stanley Cameron, Katherine N. Robertson, and Manuel A.S. Aquino, “Tetra-μ-acetato-κ8O:O’-bis[(3-chloropyridine-κN)ruthenium(II,III)](Ru—Ru) hexafluoridophosphate 1,2-dichloroethane monosolvate1”, IUCrData, 2022, 7, x220249.
61. Anthony J. Aquino, T. Stanley Cameron, Katherine N. Robertson, and Manuel A.S. Aquino, CCDC Communication (CCDC code2083050), 2021, CCDC, Cambridge, England. DOI: 10.5517/ccdc.csd.cc27xl5y
60. Fawzia O. Elnajjar, Ruiyao Wang, and Manuel A.S. Aquino, "Synthesis, Structure and Electrochemistry of Ruthenium(II) and (III) Mono- and Bis-oxalato Complexes", Inorg. Chim. Acta, 2020, 502, 119388.
59. Ruiyao Wang and Manuel A.S. Aquino, "1,3-Bis(2,4,6-trimethylphenyl)imidazolium perchlorate", IUCrData, 2019, 4, x190494.
58. Samuel A. Minaker, Ruiyao Wang, and Manuel A.S. Aquino, "1,3-Bis(2,6-diisopropylphenyl) imidazolium perchlorate", IUCrData, 2018, 3, x180516.
57. Ernest Essoun, Ruiyao Wang, and Manuel A.S. Aquino, "Disassembly of Diruthenium(II,III) Tetraacetate with P-N Donor Ligands", Inorg. Chim. Acta, 2017, 454, 97-106. [Invited manuscript for Special Issue on "Ruthenium Coordination Chemistry" in honor of Prof. K.J. Brewer].
56. Elizabeth G. Corkum, Ruiyao Wang and Manuel A.S. Aquino, "Compromising the Metal-Metal Bond in Diruthenium(II,III) Tetraacetate: Reaction of [Ru2(m-O2Me)4(MeOH)2]+ with Phosphines to Form "Ru(m-O2CMe)2(m-OMe)2Ru" Cores", Inorg. Chim. Acta, 2015, 424, 202-209. [Invited manuscript for Special Issue on "Metal-Metal Compounds and Metal Clusters" in honor of Prof. F.A Cotton].
55. Natasha F. O'Rourke, Michael Thomson, Ruiyao Wang, and Manuel A.S. Aquino, ”Tetrakis(m-n-butyrato-k8O:O')bis[(chloridorhenium(III)] (Re--Re)", Acta Cryst., 2014, E70, m349-m350.
54. Kate Dunlop, Ruiyao Wang, T. Stanley Cameron, Manuel A.S. Aquino, "Coordination of Weakly Binding Anions to [Ru2(m-O2CR)4]+ in Aqueous Solution", J. Mol. Struct., 2014, 1058, 122-129.
53. Karel G. von Eschwege, Lydia van As, Chris C. Joubert, Jannie C. Swarts, Manuel A.S. Aquino and T. Stanley Cameron, “Synthesis, Structure and Electrochemical Characterisation of a Novel Cobalt(III) tris-Dithizonato Complex”, Electrochimica Acta, 2013, 112, 747-755.
52. Brandon R. Groves, D. Ian Arbuckle, Ernest Essoun, Travis L. Lundrigan, Ruiyao Wang, and Manuel A.S. Aquino, "Chiral Induction at Octahedral Ru(II) via the Disassembly of Diruthenium(II,III) Tetracarboxylates Using a Variety of Chiral Diphosphine Ligands", Inorg. Chem., 2013, 52, 11563-11572.
51. Natasha F. O'Rourke, Michael Ronaldson, T. Stanley Cameron, Ruiyao Wang, Manuel A.S. Aquino, "Equatorial p-p Interactions in Diruthenium(II,III) Tetracarboxylate Complexes Containing Extended p-Systems", J. Mol. Struct., 2013, 1052, 17-23.
50. Luc J. Boudreau, Terri L. Clarke, Adrian H. Murray, Katherine N. Robertson, T. Stanley Cameron, and Manuel A.S. Aquino, "Sterically-Directed Disassembly of Diruthenium(II,III) Tetraacetate using Substituted and Unsubstituted 2,2'-Bipyridines and 1,10-Phenanthrolines", Inorg. Chim. Acta, 2013, 394, 152-158.
49. Karel G. Von Eschwege, Jannie C. Swarts, Manuel A.S. Aquino and T. Stanley Cameron, “(1,5-Diphenylthiocarbazonato-kS)trimethyltin(IV)”, Acta Cryst., 2012, E68, m1518.
48. Ramesh Vadavi, Eamonn D. Conrad, D. Ian Arbuckle, T. Stanley Cameron, Ernest Essoun, and Manuel A.S. Aquino, “Chiral Induction via the Disassembly of Diruthenium(II,III) Tetraacetate by Chiral Diphosphines", Inorg. Chem. , 2011, 50, 11862-11864.
47. Samuel A. Minaker, Ruiyao Wang, and Manuel A.S. Aquino, "Tetra-m-acetato-k8O:O'-bis[3-cyanopyridine-kN1)ruthenium(II,III)](Ru-Ru)hexafluoridophosphate 1,2-dichloroethane monosolvate", Acta Cryst., 2011, E67, m1554.
46. Henno J. Gericke, Nicola I. Barnard, Elizabeth Erasmus, Jannie C. Swarts, Michael J. Cook and Manuel A.S. Aquino, “Solvent and Electrolyte Effects in Enhancing the Identification of Intramolecular Electronic Communication in a Multi Redox-Active Diruthenium Tetraferrocenoate Complex, a Triple-Sandwiched Dicadmium Phthalocyanine and a Ruthenocene-Containing b-Diketone”, Inorg. Chim. Acta, 2010, 363, 2222-2232.
45. Michael Ronaldson, Chad R. Maheux, James M. Nyangulu, T. Stanley Cameron and Manuel A.S. Aquino, “12-Ethoxy-2,3,8,9-tetramethyl-benzo-[c]-phenanthradine”, Acta Cryst., 2010, E66, o124.
44. Adrian H. Murray, Zhang Yue, Andrew I. Wallbank, T. Stanley Cameron, Ramesh Vadavi, Brian J. MacLean and Manuel A.S. Aquino, “Synthesis, Structure and Electrochemistry of Mononuclear and Dinuclear Ruthenium-Thiophenecarboxylate Derivatives”, Polyhedron, 2008, 27, 1270-1279.
43. Tara J. Burchell, T. Stanley Cameron, Donal H. Macartney, Laurence K. Thompson, and Manuel A.S. Aquino, “Kinetics and Magnetism of Phosphane Diadducts of Diruthenium(II,III) Tetraacetate”, Eur. J. Inorg. Chem., 2007, 4021-4027.
42. Andrew P. White, Katherine N. Robertson, T. Stanley Cameron, Bernard V. Liengme, Daniel B. Leznoff, Simon Trudel, and Manuel A.S. Aquino, “Synthesis and Characterization of [M(DMSO)6][SnCl6] Complexes (M = Fe2+, Co2+ and Ni2+): An Old Mystery Solved”, Can. J. Chem., 2007, 85, 372-378.
41. David Wolstenholme, Manuel A.S. Aquino, T. Stanley Cameron, Joseph D. Ferrara, and Katherine N. Robertson “A Topological Analysis of the Inter-Ion Interactions of Tetraphenylphosphonium Squarate”, Can. J. Chem., 2006, 84, 804-811.
40. Ian W. Wyman, Katherine N. Robertson, T. Stanley Cameron, Jannie C. Swarts, and Manuel A.S. Aquino, “Synthesis, Structure and Electrochemistry of (Ferrocene-2-propenoato-O,O’)bis[1,2-bis(di-phenylphosphino)ethane-P,P’]ruthenium(II) Hexafluorophosphate”, Inorg. Chim. Acta, 2006, 359, 3092-3096.
39. Ian W. Wyman, Katherine N. Robertson, T. Stanley Cameron, Jannie C. Swarts, and Manuel A.S. Aquino, “Synthesis and Characterization of a Ruthenocenecarboxylate-Containing Ru(II) Complex”, Organometallics, 2005, 24, 6055-6058.
38. Brendan R.A. Bland, Heather J. Gilfoy, Katherine N. Roberston, T. Stanley Cameron, George Vanvounis and Manuel A.S. Aquino, “Hydrogen-Bonding in Diruthenium Tetraacetate Complexes with Biologically Relevent Axial Donors”, Inorg. Chim. Acta, 2005, 358, 3927-3936.
37. Jeanet Conradie, T. Stanley Cameron, Manuel A.S. Aquino, Gert J. Lamprecht and Jannie C. Swarts, “Synthetic, Electrochemical and Structural Aspects of a Series of Ferrocene-Containing Dicarbonyl Betadiketonato Rhodium(I) Complexes”, Inorg. Chim. Acta, 2005, 358, 2530-2542.
36. Ian W. Wyman, Tara J. Burchell, Katherine N. Robertson, T. Stanley Cameron, and Manuel A.S. Aquino, “Synthesis and Electrochemistry of Heterobimetallic Ferrocenecarboxylatoruthenium(II) Complexes”, Organometallics, 2004, 23, 5353-5364.
35. Manuel A.S. Aquino, “Recent Developments in the Synthesis and Properties of Diruthenium Tetracarboxylates”, Coord. Chem. Rev., 2004, 248, 1025-1045. [Citation classic, 100+ citations].
34. Manuel A.S. Aquino and Ian Wyman, “Complexes Containing Metallocene Carboxylate Ligands”, Trends in Inorganic Chemistry, 2004, 8, 1-21.
33. Michael W. Cooke, T. Stanley Cameron, Katherine N. Robertson, Jannie C. Swarts and Manuel A.S. Aquino, “Structure and Electrochemistry of Various Diruthenium(II,III) Tetrametallocene-carboxylates”, Organometallics, 2002, 21, 5962-5971.
32. Mark B. Twitchett, Gerhard Schenk, Manuel A.S. Aquino, Douglas T.-Y. Yiu, Tai-Chu Lau and A.Geoffrey Sykes, “Reactivity of MII Metal-Substituted Derivatives of Pig Purple Acid Phosphatase (Uteroferrin) with Phosphates”, Inorg. Chem., 2002, 41, 5787-5794.
31. Michael W. Cooke, Heather J. Gilfoy, Christopher A. Murphy, T. Stanley Cameron, Ellen J. Beck, George Vamvounis and Manuel A.S. Aquino, “Synthesis and Crystal Structures of Urea and Thiourea Derivatives of Diruthenium(II,III) Tetraacetate”, Polyhedron, 2002, 21, 1235-1244.
30. Constance E.J. van Rensburg, Elke Kreft, Sean R. Dalrymple, Denise M. MacDonald, Michael W. Cooke, Jannie C. Swarts and Manuel A.S. Aquino, “Cytotoxicity of a Series of Water-Soluble Mixed-Valent Diruthenium Tetracarboxylates”, Anticancer Res., 2002, 22, 889-892.
29. Heather J. Gilfoy, Katherine N. Robertson, T. Stanley Cameron and Manuel A.S. Aquino, “Synthesis and Structure of the First Sulphur-Donor Adduct of a Diruthenium Tetracarboxylate”, Inorg. Chim. Acta., 2002, 331, 330-335. [Invited manuscript for Special Issue in honor of Prof. A.G. Sykes].
28. Heather J. Gilfoy, Katherine N. Robertson, T. Stanley Cameron and Manuel A.S. Aquino, “Tetra-m-acetato-O:O’-bis(quinoline-N)diruthenium(II,III) hexafluorophosphate quinoline solvate”, Acta Cryst., 2001, E57, m496-m497.
27. Glen G. Briand, Michael W. Cooke, T. Stanley Cameron, Heather M. Farrell, Tara J. Burchell and Manuel A.S. Aquino, “An Axial Phosphine Diadduct of Diruthenium(II,III) Tetraacetate”, Inorg. Chem., 2001, 40, 3267-3268.
26. Michael W. Cooke, Christopher A. Murphy, T. Stanley Cameron, Jannie C. Swarts and Manuel A.S. Aquino, “Structure and Electrochemistry of Diruthenium (II,III) Tetraferrocenecarboxylate: Evidence for Ferrocenyl-Ferrocenyl Communication”, Inorg. Chem. Commun., 2000, 3, 721-725.
25. Christopher A. Murphy, T. Stanley Cameron, Michael W. Cooke and Manuel A.S. Aquino, "Synthesis and Structure of trans-Dimethylammonium Bis(oxalato)diaquaruthenate(III) Tetrahydrate”, Inorg. Chim. Acta, 2000, 305, 225-229.
24. George Vamvounis, Jennifer F. Caplan, T. Stanley Cameron, Katherine N. Robertson and Manuel A.S. Aquino, "Synthesis, Structure and Electrochemistry of Nitrogen Base Adducts of Tetraacetatodiruthenium (II,III): Dependence of Redox Potential and Ru-Ru Bond Length on Axial Ligand Donor Strength", Inorg. Chim. Acta, 2000, 304, 87-98.
23. W.C. (Ina) du Plessis, Johannes J.C. Erasmus, Gert J. Lamprecht, Jeanet Conradie, T. Stanley Cameron, Manuel A.S. Aquino and Jannie C. Swarts, "Cyclic Voltammetry of Ferrocene-Containing b-Diketones as a Tool to Obtain Group Electronegativities. The Structure of 3-Ferrocenoyl-2-Hydroxy-1,1,1-Trifluoroprop-2-ene", Can. J. Chem., 1999, 77, 378-386.
22. Jennifer F. Caplan, Christopher A. Murphy, Susan Swansburg, Robert P. Lemieux, T. Stanley Cameron and Manuel A.S. Aquino, "Evidence of Room Temperature Mesomorphism in a Mixed-Valent Diruthenium(II,III) Quinta-palmitoleate Polymer", Can. J. Chem., 1998, 76, 1520-1523.
21. Ellen J. Beck, Krista D. Drysdale, Laurence K. Thompson, Licun Li, Christopher A. Murphy and Manuel A.S. Aquino, "Weak Intermolecular Antiferromagnetic Exchange in {[Ru2(O2CCH3)4(L)]X}n Polymers (L = 4,4'-Dipyridine and 1,4-Diazabicyclooctane, X = PF6- or BPh4-)", Inorg. Chim. Acta., 1998, 279, 121-125.
20. Manuel A.S. Aquino, "Diruthenium and Diosmium Tetracarboxylates: Synthesis, Physical Properties and Applications", Coord. Chem. Rev., 1998, 170, 141-202. [Citation classic, 100+ citations].
19. Krista D. Drysdale, Ellen J. Beck, T. Stanley Cameron, Kathy N. Robertson and Manuel A.S. Aquino, “Crystal Structures and Physico-Chemical Properties of a Series of Mixed-Valent [Ru2(O2CCH3)4L2](PF6) Adducts (L = H2O, DMF, DMSO)”, Inorg. Chim. Acta, 1997, 256, 243-252.
18. Manuel A.S. Aquino, Christopher A. White, Corinne Bensimon, J.E. Greedan and Robert J. Crutchley, “A Pentaammineruthenium(III) Dimer with the Novel Bridging Ligand 4,4’-Dicyanamidobiphenyl Dianion”, Can. J. Chem., 1996, 74, 2201-2208.
17. Joo-Sang Lim, Manuel A.S. Aquino and A. Geoffrey Sykes, “Mechanistic Studies on the Reactions of Mo(VI), W(VI), V(V) and As(V) Tetraoxo-Anions with the Fe(II)Fe(III) form of Purple Acid Phosphatase from Porcine Uteri (Uteroferrin)”, Inorg. Chem., 1996, 35, 614-618.
16. Manuel A.S. Aquino, Joo-Yeon Han, Jannie C. Swarts and A.Geoffrey Sykes, “Mechanistic Studies on the Binuclear Fe Enzymes Ribonucleotide Reductase and Purple Acid Phosphatase”, D.P Kessissogiou (Ed.), in Bioinorganic Chemistry, Kluwer Academic Publishers, Holland, 1995, 57-65.
15. Manuel A.S. Aquino, William Clegg, Qiu-Tian Liu and A. Geoffrey Sykes, "Structure of Hexaaquatitanium(III) p-Toluenesulfonate Trihydrate", Acta Crystallogr., Sect. C., 1995, 51, 560-562.
14. Jannie C. Swarts, Manuel A.S. Aquino, Joo-Yeon Han, Kin-Yu Lam and A. Geoffrey Sykes, "Kinetic Studies on the Reduction of the Tyrosyl Radical of the R2 Subunit of E. coli Ribonucleotide Reductase", Biochim. Biophys. Acta, 1995, 1247, 215-224.
13. Manuel A.S. Aquino and A. Geoffrey Sykes, "Redox Reactivity of the Binuclear Iron Active Site of Porcine Purple Acid Phosphatase (Uteroferrin)", J. Chem. Soc., Dalton Trans., 1994, 683-687.
12. Manuel A.S. Aquino, Joo-Sang Lim and A. Geoffrey Sykes, "Mechanism of the Reaction of Different Phosphates with the Fe(II)Fe(III) form of Purple Acid Phosphatase from the Porcine Uterus (Uteroferrin)", J. Chem. Soc., Dalton Trans., 1994, 429-436.
11. Manuel A.S. Aquino, Robert J. Crutchley, Florence L. Lee, Eric J. Gabe and Corinne Bensimon, "Crystal Structures of 1,4-Dicyanomidobenzene Dianion Derivatives", Acta Crystallogr., Sect. C., 1993, 49, 1543-1547.
10. Manuel A.S. Aquino, Joo-Sang Lim and A. Geoffrey Sykes, "Mechanism of the Reaction of Phosphate with Purple Acid Phosphatase", J. Chem. Soc., Dalton Trans., 1992, 2135-2136.
9. Manuel A.S. Aquino, Florence L. Lee, Eric J. Gabe, Corinne Bensimon, John E. Greedan and Robert J. Crutchley, "Superexchange Metal-Metal Coupling in Dinuclear Pentaammineruthenium Complexes Incorporating a 1,4-Dicyanamidobenzene Dianion Bridging Ligand", J. Am. Chem. Soc., 1992, 114, 5130-5140.
8. Manuel A.S. Aquino, "Synthesis of Dinuclear Pentaammineruthenium Complexes Bridged by Dicyanamidobenzene Ligands", Ph.D. Thesis, Carleton University Press, Ottawa, Ontario, 1991, 149 pp.
7. Manuel A.S. Aquino, Florence L. Lee, Eric J. Gabe, John E. Greedan and Robert J. Crutchley, "Long-Range Antiferromagnetic Coupling Between Two Ruthenium(III) Ions Bridged by a 1,4-Dicyanamidobenzene Dianion Ligand", Inorg. Chem., 1991, 30, 3234-3236.
6. Robert J. Crutchley, Akila A. Saleh, Kierstan McCaw and Manuel A.S. Aquino, "Dependence of Ligand to Metal Charge-Transfer Oscillator Strength on the Nature of the Ruthenium(III)-Cyanamide Bond", Mol. Cryst. Liq. Cryst., 1991, 194, 93-101.
5. Manuel A.S Aquino, Ann E. Bostock and Robert J. Crutchley, "A Pentaammineruthenium Mixed-Valence Complex with 1,4-Dicyanamido-2,3,5,6-tetrachlorobenzene Dianion as Bridging Ligand", Inorg. Chem., 1990, 29, 3641-3644.
4. Manuel A.S. Aquino, Daniel A. Foucher and Donal H. Macartney, "Electron-Exchange and Electron-Transfer Reactions Involving the Dirhodium(II) Tetraacetate Couple in Acetonitrile", Inorg. Chem., 1989, 28, 3357-3361.
3. Manuel A.S. Aquino and Donal H. Macartney, "Ligand Substitution Reactions of Dirhodium(II) Tetraacetate with Water-Soluble Phosphines", Inorg. Chem., 1988, 27, 2868-2872.
2. Manuel A.S. Aquino and Donal H. Macartney, “Axial-Ligand Substitution Reactions of Dirhodium(II) Tetraacetate with Phosphines and Phosphites in Acetonitrile”, Inorg. Chem., 1987, 26, 2696-2700.
1. Manuel A.S. Aquino, " Ligand Substitution and Electron Transfer Reactions of Rh2(m-O2CCH3)4 Complexes", M.Sc. Thesis, Queen's University Press, Kingston, Ontario, 1987, 150 pp.
