Synthesis and Reactivity of Molybdenum Complexes Containing Functionalized Alkynyl Ligands: A Photochemically Activated CO-Releasing Molecule (PhotoCO-RM)

Reaction of [MoCl(η5-C5H5)(CO)3] with propargyl alcohols HC≡CCR1R2OH in the presence of catalytic amounts of CuI and using NEt2H as solvent results in the formation of alkynyl complexes [Mo(C≡CCR1R2OH)(η5-C5H5)(CO)3]. The structure of the complexes where R1 = R2 = Me and R1 = Me, R2 = Ph were confirmed by single-crystal X-ray diffraction. The method could be extended to a range of propargyl ethers and propargyl esters, which allowed for the preparation of molybdenum complexes containing pendant salicylate and β-d-fructopyranose groups. The alkynyl complex [Mo(C≡CCH2OH)(η5-C5H5)(CO)3] undergoes a further reaction with NEt2H to give the substituted allyl complex [Mo(η3-H2CC{NEt2}CHC{O}NEt2)(η5-C5H5)(CO)3]. Similar products could be obtained from the reaction of [MoCl(η5-C5H5)(CO)3] with HC≡CCH2OH in the presence of CuI using pyrrolidine or piperidine as solvent. In the case of the reaction with piperidine a further product could be isolated that has arisen from the coupling of two propargyl alcohol molecule...

[1]  R. Motterlini,et al.  A re-investigation of [Fe(L-cysteinate)2(CO)2]2-: an example of non-heme CO coordination of possible relevance to CO binding to ion channel receptors. , 2011, Dalton transactions.

[2]  U. Schatzschneider.  PhotoCORMs: Light-triggered release of carbon monoxide from the coordination sphere of transition metal complexes for biological applications , 2011 .

[3]  Q. Dou,et al.  Synthesis, characterization, and reactivity of the stable iron carbonyl complex [Fe(CO)(N4Py)](ClO4)2: photoactivated carbon monoxide release, growth inhibitory activity, and peptide ligation. , 2011, Inorganic chemistry.

[4]  Jason M. Lynam,et al.  Modification of the deoxy-myoglobin/carbonmonoxy-myoglobin UV-vis assay for reliable determination of CO-release rates from organometallic carbonyl complexes. , 2011, Dalton transactions.

[5]  O. Blacque,et al.  Reactivity of 17 e- complex [Re(II)Br4(CO)2]2- with bridging aromatic ligands. Characterization and CO-releasing properties. , 2011, Dalton transactions.

[6]  H. Adams,et al.  [Mn(CO)4{S2CNMe(CH2CO2H)}], a new water-soluble CO-releasing molecule. , 2011, Dalton transactions.

[7]  P. Mascharak,et al.  Designed iron carbonyls as carbon monoxide (CO) releasing molecules: rapid CO release and delivery to myoglobin in aqueous buffer, and vasorelaxation of mouse aorta. , 2011, Inorganic chemistry.

[8]  S. Amslinger,et al.  Acyloxybutadiene iron tricarbonyl complexes as enzyme-triggered CO-releasing molecules (ET-CORMs). , 2011, Angewandte Chemie.

[9]  M. Eberlin,et al.  Tetrachlorocarbonyliridates: water-soluble carbon monoxide releasing molecules rate-modulated by the sixth ligand. , 2011, Inorganic chemistry.

[10]  H. Lang,et al.  Homoleptic transition metal acetylides , 2011 .

[11]  Jason M. Lynam,et al.  Group 6 carbon monoxide-releasing metal complexes with biologically-compatible leaving groups. , 2010, Inorganic chemistry.

[12]  H. Adams,et al.  Iron indenyl carbonyl compounds: CO-releasing molecules. , 2010, Dalton transactions.

[13]  Jason M. Lynam.  Recent mechanistic and synthetic developments in the chemistry of transition-metal vinylidene complexes. , 2010, Chemistry.

[14]  A. Bogdanova,et al.  CO releasing properties and cytoprotective effect of cis-trans-[Re(II)(CO)2Br2L2]n complexes. , 2010, Inorganic chemistry.

[15]  V. V. Krivykh,et al.  Cationic η3-butadienyl complexes of chromium and manganese , 2010 .

[16]  U. Schatzschneider.  Photoactivated Biological Activity of Transition‐Metal Complexes , 2010 .

[17]  H. Richter,et al.  A photochemical precursor for carbon monoxide release in aerated aqueous media. , 2010, Inorganic chemistry.

[18]  B. Mann.  Carbon Monoxide: An Essential Signalling Molecule , 2010 .

[19]  B. Spingler,et al.  Tricarbonylmanganese(I) and –rhenium(I) Complexes of Imidazol‐Based Phosphane Ligands: Influence of the Substitution Pattern on the CO Release Properties , 2009 .

[20]  U. Schatzschneider,et al.  Sonogashira and "Click" reactions for the N-terminal and side-chain functionalization of peptides with [Mn(CO)3(tpm)]+-based CO releasing molecules (tpm = tris(pyrazolyl)methane). , 2009, Dalton transactions.

[21]  Jason M. Lynam,et al.  Diversity and design of metal-based carbon monoxide-releasing molecules (CO-RMs) in aqueous systems: revealing the essential trends. , 2009, Dalton transactions.

[22]  Jason M. Lynam,et al.  Mu2-alkyne dicobalt(0)hexacarbonyl complexes as carbon monoxide-releasing molecules (CO-RMs): probing the release mechanism. , 2009, Dalton transactions.

[23]  R. Gust,et al.  Photoinduced CO release, cellular uptake and cytotoxicity of a tris(pyrazolyl)methane (tpm) manganese tricarbonyl complex. , 2008, Chemical communications.

[24]  P. Mathur,et al.  Mixed Metal Acetylide Complexes , 2008 .

[25]  H. Adams,et al.  [(η-C5H4R)Fe(CO)2X], X = Cl, Br, I, NO3, CO2Me and [(η-C5H4R)Fe(CO)3]+, R = (CH2)nCO2Me (n = 0–2), and CO2CH2CH2OH: a new group of CO-releasing molecules , 2007 .

[26]  R. Motterlini,et al.  CO and NO in medicine. , 2007, Chemical communications.

[27]  W. Wong.  Mercury alkynyls as versatile templates for new organometallic materials and polymers , 2007 .

[28]  Jason M. Lynam,et al.  Eta(1)-2-pyrone metal carbonyl complexes as CO-releasing molecules (CO-RMs): a delicate balance between stability and CO liberation. , 2007, Dalton transactions.

[29]  J. Saillard,et al.  Alkynyl ruthenium colorimetric sensors: optimizing the selectivity toward fluoride anion. , 2007, Inorganic chemistry.

[30]  S. Coles,et al.  One pot synthesis of η3-butadienyl complexes of Mo(II) or W(II): Crystal structure of [MoCl(CO)2(η3-CH2C(CONHCH2CCH)CCH2)(2,2′-bipyridine)] , 2007 .

[31]  H. Adams,et al.  Metal carbonyls as pharmaceuticals? [Ru(CO)3Cl(glycinate)], a CO-releasing molecule with an extensive aqueous solution chemistry. , 2007, Dalton transactions.

[32]  Jason M. Lynam,et al.  Bioactive Properties of Iron-Containing Carbon Monoxide-Releasing Molecules , 2006, Journal of Pharmacology and Experimental Therapeutics.

[33]  Jason M. Lynam,et al.  Eta4-pyrone iron(0)carbonyl complexes as effective CO-releasing molecules (CO-RMs). , 2006, Bioorganic & medicinal chemistry letters.

[34]  T. Ren.  Diruthenium σ-Alkynyl Compounds: A New Class of Conjugated Organometallics , 2005 .

[35]  M. Humphrey,et al.  Alkynyl compounds and nonlinear optics , 2004 .

[36]  Y. Wakatsuki.  Mechanistic aspects regarding the formation of metal vinylidenes from alkynes and related reactions , 2004 .

[37]  V. Cadierno,et al.  Synthesis and reactivity of α,β-unsaturated alkylidene and cumulenylidene Group 8 half-sandwich complexes , 2004 .

[38]  C. Leffler,et al.  The permissive role of endothelial NO in CO-induced cerebrovascular dilation. , 2004, American journal of physiology. Heart and circulatory physiology.

[39]  R. Foresti,et al.  Vasoactive properties of CORM‐3, a novel water‐soluble carbon monoxide‐releasing molecule , 2004, British journal of pharmacology.

[40]  C. E. Powell,et al.  Nonlinear optical properties of transition metal acetylides and their derivatives , 2004 .

[41]  F. Fenoy,et al.  Acute renal hemodynamic effects of dimanganese decacarbonyl and cobalt protoporphyrin. , 2004, Kidney international.

[42]  P. Low,et al.  Transition Metal Complexes Containing All-Carbon Ligands , 2004 .

[43]  C. Leffler,et al.  Role of cGMP in carbon monoxide-induced cerebral vasodilation in piglets. , 2004, American journal of physiology. Heart and circulatory physiology.

[44]  R. Foresti,et al.  Metal carbonyls: a new class of pharmaceuticals? , 2003, Angewandte Chemie.

[45]  Charlotte K. Williams,et al.  Metal alkynyl σ complexes: Synthesis and materials , 2003 .

[46]  C. Day,et al.  Preparation and Characterization of Molybdenum Tris(pyrazolyl)borate Dicarbonyl η3-Dienyl Complexes , 2003 .

[47]  P. Sarathchandra,et al.  Carbon Monoxide-Releasing Molecules: Characterization of Biochemical and Vascular Activities , 2002, Circulation research.

[48]  S. Conejero,et al.  Activation of Propargylic Alcohols Derived from Hormonal Steroids by the Indenyl−Ruthenium(II) Complex [RuCl(η5-C9H7)(PPh3)2]: Experimental and Theoretical Evidence of an Allenylidene−Vinylvinylidene Equilibrium , 2002 .

[49]  P. Low,et al.  Transition Metal Chemistry of 1,3-Diynes, Poly-ynes, and Related Compounds , 2001 .

[50]  R. Gust,et al.  Acetylenehexacarbonyldicobalt complexes, a novel class of antitumor drugs , 2000 .

[51]  R. S. Liu,et al.  Synthesis of Heterocyclic and Carbocyclic Compounds via Alkynyl, Allyl, and Propargyl Organometallics of Cyclopentadienyl Iron, Molybdenum, and Tungsten Complexes. , 2000, Chemical reviews.

[52]  Li,et al.  Facile synthesis of oxa- and azacyclic dienes via cycloalkenation of alkynyltungsten compounds. Stereoselective construction of tricyclic furan and pyran derivatives via intramolecular diels-alder reaction , 2000, The Journal of organic chemistry.

[53]  Mark E. Smith,et al.  Heterometallic complexes containing C4 chains. X-ray structures of {Cp(OC)3W}CCCC{Ir(CO)(PPh3)2(O2)} and cis-Pt{CCCC[W(CO)3Cp]}2(PEt3)2 , 2000 .

[54]  Rai‐Shung Liu,et al.  Efficient Synthesis of Bicyclic Lactones via Tungsten-Mediated Intramolecular Cycloalkenation. , 1998, The Journal of organic chemistry.

[55]  D. Braga,et al.  X−H---π (X = O, N, C) Hydrogen Bonds in Organometallic Crystals , 1998 .

[56]  Yu Wang,et al.  Unexpected regioselectivity in the coupling of π-coordinated tritylallene with an amido ligand in molybdenum complex , 1998 .

[57]  M. Humphrey,et al.  Bonding of η1-Acetylide Ligands to Electron-Rich Ruthenium Centers: Can Electron-Withdrawing Ligands Induce Significant Metal-to-Ligand Back-Bonding? , 1997 .

[58]  S. Peng,et al.  Tungsten(II)−Carbene Complex Functions as a Dicationic Synthon: Efficient Constructions of Furan and Pyran Frameworks from Readily Available α,δ- and α,ε-Alkynols , 1997 .

[59]  Yancey D. Ward,et al.  Synthesis and Characterization of Stable Cationic [Hydrotris(1-pyrazolyl)borato]Mo(CO)(NO)(η3-allyl) ComplexesSolid-State and Solution Evidence for an η2-Allyl Structure , 1996 .

[60]  M. Lanfranchi,et al.  Synthesis and characterization of novel neutral σ-alkynylcarbonylnitrosyl molybdenum(0) and tungsten(0) complexes. Crystal structure of [Mo(CCnPr) (CO)2 (dppe) (NO)] [dppe = 1,2-bis(diphenylphosphino) ethane] , 1996 .

[61]  P. Low,et al.  Syntheses of metal diynyl complexes: novel routes to all-carbon ligands , 1996 .

[62]  M. D. Hopkins,et al.  The Bonding of Metal-Alkynyl Complexes , 1996 .

[63]  R. Walton,et al.  Transition metal butadienyl complexes , 1995 .

[64]  Yu Wang,et al.  Reactivity of a Tungsten Carbonyl .sigma.-Allenyl Complex: Regiospecific C-C Bond Formation and Structure of Azatungstacyclobutane and Oxatungstacyclopentene Complexes , 1994 .

[65]  H. Rzepa,et al.  A crystallographic AM1 and PM3 SCF-MO investigation of strong OH ⋯π-alkene and alkyne hydrogen bonding interactions , 1994 .

[66]  E. Tiekink,et al.  Cyclopentadienyl-ruthenium and -osmium chemistry: XXXIX. Syntheses of novel alkynyl-ruthenium complexes. X-Ray structures of two forms of {Ru(PPh3)2(η-C5H5)}2(μ-C4) and of Ru{CCC(O)Me}(PPh3)2(η-C5H5)☆ , 1993 .

[67]  Ying-Chih Lin,et al.  Synthesis and reactions of tungsten carbonyl complexes containing .beta.-(chlorocarbonyl)allylic ligands , 1993 .

[68]  M. Mcpartlin,et al.  Reactions of co-ordinated ligands. Part 54. Synthesis of (1,2,3-η)-trans-butadienyl complexes by deprotonation or desilylation of cationic molybdenum 1,3-diene complexes; formation of η4-vinylketene complexes and crystal structures of [Mo{(1,2,3-η)-trans-CH2CHCCH2}(CO)2(η-C5Me5)], [Mo{η3-CH2CC(Me)CH , 1992 .

[69]  M. Mahon,et al.  Synthetic and molecular orbital study of .eta.3(3e)-butadienyl complexes of molybdenum , 1991 .

[70]  M. Lanfranchi,et al.  Synthesis and characterization of novel σ-alkynyl cyclopentadienyl iron(II) complexes [Fe(CCR)L2(η-C5H5)] [L CO; L2 bis(diphenylphosphino)methane (dppm)]. Crystal structure of [Fe(CCC6H5)(dppm)(η-C5H5)] , 1991 .

[71]  M. Bruce.  Organometallic Chemistry of Vinylidene and Related Unsaturated Carbenes , 1991 .

[72]  Yu Wang,et al.  Distinct chemical reactivities of tungsten propargyl and allenyl complexes: novel carbon-carbon bond formation of the allenyl ligand and molecular structure of a tungsten complex containing an azametallacyclobutane ring , 1991 .

[73]  M. R. Mazzieri,et al.  Controlling the regiochemistry of nucleophilic attack on unsymmetrical allyl complexes , 1990 .

[74]  M. W. Whiteley,et al.  Synthetic and electrochemical studies on alkynyl complexes of iron and ruthenium , 1987 .

[75]  D. Collison,et al.  The Chemistry of Cycloheptatrienyl Complexes of Molybdenum and Tungsten: the Synthesis and Reactions of some Vinylidene and Alkynyl Derivatives , 1987 .

[76]  V. Riera,et al.  Synthesis of manganese(I) carbonyls with σ-bonded alkynyl ligands , 1985 .

[77]  J. Matisons,et al.  Some more transition metal acetylides , 1984 .

[78]  J. Faller,et al.  Distortions in trihapto-allyls induced by electronic asymmetry: A comparison of the structures of (η5-C5H5)Mo(CO)2(η3-C3H5) and (η5-C5H5)Mo(NO(I)(η3-C3H5) , 1980 .

[79]  R. Hoffmann,et al.  Effect of ligand asymmetry on the structure and reactivity of CpMLL'(allyl) (Cp = cyclopentadienyl, M = metal, L = ligand) and -(ethylene) complexes , 1979 .

[80]  J. Faller,et al.  Organometallic conformational equilbria : XVI. Steric effects on π-allyl and π-indenyl orientation in molybdenum and tungsten complexes , 1973 .

[81]  G. Wilkinson,et al.  Alkyl and aryl derivatives of π-cyclopentadienyl compounds of chromium, molybdenum, tungsten, and iron , 1956 .