A Review on the Characterization of Dinitrogen Substituted Cyclopentadienyl Manganese Tricarbonyl (CpMn(CO3)N2)
DOI:
https://doi.org/10.54117/k221ge96Keywords:
Dinitrogen, Characterisation, Photolysis, Infrared Spectroscopy, Raman Spectroscopy, Organometallic complexes, Bonding ModesAbstract
This review details the use of Fourier Transform Infrared (FTIR) and Raman Spectroscopic methods, to characterize dinitrogen complexes formed following the photolysis of cyclopentadienyl manganese tricarbonyl ((ƞ5-C5H5)Mn(CO)3), in the presence of N2. The review was performed to explore the information relating to the structure and bonding modes of dinitrogen to the metal Centre. The main aim here was to explore the utilization of Raman spectroscopy in complimenting the application of Infrared spectroscopy in the characterization of organometallic complexes.
References
Adams, D. M., & Squire, A. (1973). Re-Assignment of The Vibrational Spectra of Rr-Cyclopentadienyl Manganese Tricarbonyl. J. Organomet. Chem., 63, 381-388.
Banister, J. A., George, M. W., Grubert, S., Howdle, S. M., Jobling, M., Johnson, F. P. A., Westwell, J. R. (1994). Organometallic photochemistry in supercritical fluids: reactions of cyclopentadienyl carbonyl and phosphine carbonyl complexes of manganese with dinitrogen. J. Organomet. Chem., 484, 129-135.
Bitterwolf, T. E., Lott, K. A., Rest, A. J., & J. Mascetti. (1991). Photolysis of Group VI metal carbonyls, (C6H6)Cr(CO)3, (C5H5)Mn(CO)3, (CH3C5H4)Mn(CO)3 and (C5H5)Re(CO)3 in Nujol at 77K. J. Organomet. Chem., 419, 113-126.
Bloyce, P. E., Hooker, R. H., Rest, A. J., Bitterwolf, T. E., Fitzpatrick, N. J., & Shade, J. E. (1990). Photochemistry of some Manganese and Chromium Dinuclear Metal Carbonyl complexes in frozen gas matrices. J. Chem. Soc., Dalton Trans., 833-841.
Brian, C. S. (2011). Fundamentals of Fourier Transform Infrared Spectroscopy (Second ed.). London: CRC Press, 25-50
Butler, I. S., & Harrod, J. F. (1989). Inorganic Chemistry Principle and Application. Redwood City: The Benjamin/Cummings Publishers. 110-139
Calladine, J. A., Torres, O., Anstey, M., Ball, G. E., Bergman, R. G., Curley, J., . . . Peter, C. (2010). Photoinduced N2 loss as a route to long-lived organometallic alkane complexes: A time-resolved IR and NMR study. Chem. Sci., 1(5), 622-630.
Calladine, J. A., Vuong, K. Q., Sun, X. Z., & George, M. W. (2009). Recent advances in organometallic alkane and noble gas complexes. Pure Appl. Chem., 81(9), 1667-1675.
Chatt, J., Dilworth, J. R., & Richards, R. L. (1978). Recent Advances in the Chemistry of Nitrogen Fixation. Chem. Rev., 78(6), 589-625.
Childs, G. I., Colley, C. S., Dyer, J., Grills, D. C., Sun, X. Z., Yang, J., & M.W. George. (2000). Investigation into the reactivity of M(η5-C5R5)(CO)2(alkane) (M = Mn or Re; R = H, Me or Ph; alkane = n-heptane or cyclopentane) and Re(η5-C5H5)(CO)2(Xe) in solution at cryogenic and room temperature. J. Chem. Soc., Dalton Trans., 12, 1901-1906.
Childs, G. I., Gallagher, S., Bitterwolf, T. E., & George, M. W. (2000). An inve stigation into the photochemical reactions of M(η5-C5H5)(CO)4 and M(η5-C9H7)(CO)4 (M = Nb or Ta) with H2 and N2 in polyethylene matrices and liquid xenon at low temperature. J. Chem. Soc., Dalton Trans., 24, 4534-4541.
Clarke, M. J., Cooper, A. I., Howdle, S. M., & Poliakoff, M. (2000). Photochemical Reactions of Organometallic Complexes Impregnated into polymer, Speciation, Isomerization and hydrogenation of residual Alkene moieties in polythylene. J. Am. Chem. Soc., 122, 2523-2531.
Clarke, M. J., Howdle, S. M., Jobling, M., & Poliakoff, M. (1994). Photochemical Generation of Polymer-Bound CpMn(CO)2 Complexes in Polyethylene Film. A diagonostic tool for investigating the Unsaturation of the polymer. J. Am. Chem. Soc., 116, 8621-8628.
Cooper, A. I., Howdle, S. M., Hughes, C., Jobling, M., Kazarian, S. G., Poliakoff, M., Johnston, K. P. (1993). Spectroscopic Probes for Hydrogen Bonding, Extraction Impregnation and Reaction in Supercritical Fluids. ANALYST, 118, 1111-1116.
Cotton, F. A., Wilkinson, G., & Gaus, P. L. (1995). Basic Inorganic Chemistry (3rd ed.). New York: John Wiley and sons. 105-210.
Cowan, A. J., & George, M. W. (2008). Formation and reactivity of organometallic alkane complexes. Coord. Chem. Rev., 252(23-24), 2504-2511.
Creaven, B. S. D., A. J. Kelly, J. M. Long, C. and Poliakoff, M. (1987). Structure and Reactivity of (C5H5)Mn(CO)2 in Room Temperature Solution. Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time Resolved Infrared Spectroscopy. Organomet., 6, 2600-2605.
Das, R. S., & Agrawal, Y. K. (2011). Raman spectroscopy: Recent advancements, techniques and applications. Vib. Spectrosc., 57(2), 163-176.
Durig, J. R., Marston, A. L., King, R. B., & Houk, L. W. (1969). The Infrared and Raman Spectra Of Cyclopentadienylvanadium Tetracarbonyl Derivatives: Evaluation Of The Carbon-Oxygen Force Constants. J. Organomet. Chem., 16 425-437.
Easun, T. L., Jia, J., Calladine, J. A., Blackmore, D. L., Stapleton, C. S., Vuong, K. Q., George, M. W. (2014). Photochemistry in a 3D metal-organic framework (MOF): monitoring intermediates and reactivity of the fac-to-mer photoisomerization of Re(diimine)(CO)3Cl incorporated in a MOF. Inorg. Chem., 53(5), 2606-2612. Retrieved from https://www.ncbi.nlm.nih.gov/pubmed, 2451-2024
Ferraro, J. R., & Nakamoto, K. (1994). Introductory Raman Spectroscopy (K. Nakamoto Ed. Second Edition ed.). Boston: Academic Press.
Fitzpatrick, N. J., & Mathews, N. J. (1973). Theoretical studies of nitrogen bonded organometallic carbonyls. J. Organomet. Chem., 61, C45-C47.
Fitzpatrick, P. J., Page, Y. L., Sedman, J., & Butler, I. S. (1981a). Reexamination Of The Crystal and Molecular Structure Of Tricarbonyl(~5-Cyclopentadienyl)Manganese(I) Structural and Spectroscopic Evidence. Inorg. Chem., 20(9), 2852-2861.
Fitzpatrick, P. J., Page, Y. L., Sedman, J., & Butler, I. S. (1981b). The Structure Of Tricarbonyl(Rf-Cyclopentadienyl)Rhenium(I). Acta Cryst., B37, 1052-1058.
George, M. W., Kuimova, M. K., Matousek, P., Wilson, C., Alsindi, W. Z., Parker, A. W., P. Portius. (2003). Using picosecond and nanosecond time-resolved infrared for the nvbistigation of excited state and reaction intermediates of inorganic systems. Dalton Trans., 3996-4006.
George, M. W., & Turner, J. J. (1998). Excited states of transition metal complexes studied by time resolved infrared spectroscopy. Coord. Chem. Rev., 177, 201–217.
Grills, D. C., Huang, K. W., Muckerman, J. T., & E. Fujita. (2006). Kinetic studies of the photoinduced formation of transition metal–dinitrogen complexes using time-resolved infrared and UV–vis spectroscopy. Coord. Chem. Rev., 250(13-14), 1681-1695.
Hermann, H., Grevels, F. W., Henne, A., & Schaffner, K. (1982). Flash Photolysis with Infrared Detection. The Photochemistry and Secondary Thermal Reaction of M(CO)6 [M=Cr, Mo and W]. J. Phys. Chem., 86, 5151-5154.
Hill, R. H., & Wrighton, M. S. (1987). Oxidative Addition of Trisubstituted Silanes to Photochemically Generated Coordinatively Unsaturated Species (C4H4)Fe(CO), CpMn(CO)2 and (C6H6)Cr(CO)2 and Related Molecules Organomet., 6, 632-638.
Hitam, R. B., K.A.Mahmoud, & Rest, A. J. (1984). Matrix Isolation Studies of Organometallic Intermediates. Coord. Chem. Rev., 55, 1-29.
Howdle, S. M., Grebenik, P., Perutz, R. N., & Poliakoff, M. (1989). The synthesis and spectroscopic identification of CpRe(N2)3 and CpReCO(N2)2 in supercritical Xenon at room temperature and in N2 Matrices at 20K. J. Chem. Soc. Chem. Commun., 1517-1519.
Howdle, S. M., & Poliakoff, M. (1989). Organometallic Photochemistry in Supercritical Fluids the Reaction of H2 with [CpM(CO)3] (M=Re and Mn) and the formation of a non clasical dihydrogen complex of Manganase(I). J. Chem. Soc., Chem. Commun., 1099-1101.
Hyams, I. J., Bailey, R. T., & Lippincott, E. R. (1967). The infrared and Raman spectra of clopentadienyl compounds (cyclopentadienyl manganese tricarbonyl). Spectrochim. Acta., 2(3A), 273-284.
Johnson, F. P. A., Gordon, C. M. P., Hodges, M., Poliakoff, M., & J.J. Turner. (1991). Photochemistry of [M(q5-C5H,)(CO),Et] (M = Mo or W) a mechanistic study using time resolved infrared spectroscopy and matrix isolation. J. Chem. Soc., Dalton Trans., 833-839.
Kariuki, D., & Kettle, S. F. A. (1976). The Raman Spectra. of Mixed Crystals-of Metal Carbonyls In The 2000 Cm-1 Region. J. Organomet. Chem., 105, 206-215.
Kelly, J. M., & Gustorf, E. K. V. (1973). Observation of pentacarbonylchromium on flash photolysis of hexacarbonylchromium in cyclohexane solution J. Chem. Soc. Chem. Commun., 105–106.
Kemnitz, C. R., Ball, E. S., & McMahon, R. J. (2011). Photochemistry of CpMn(CO)3 and Related Derivatives: Spectroscopic Observation of Singlet and Triplet CpMn(CO)2. Organomet., 31(1), 70-84.3.
Kettle, S. F. A. (2007). Symmetry and Structure Readable Group Theory for Chemists (Third ed.). West Sussex: John Wiley and Sons. 95-106.
Kurimura, Y., Uchino, Y., Ohta, F., Saito, C., Koide, M., & Tsuchida, E. (1981). Preparation of polymer bound dinitrogen complexes by direct reactions of polymer metal complexes with molecular nitrogen. Polymer J., 13(3), 247-253.
Leitner, W. (2002). Supercritical Carbon Dioxide as a Green Reaction Medium for Catalysis. Acc. Chem. Res. (35), 746-756.
Maier, W. B., Poliakof, M., Simpson, M. B., & Turner, J. J. (1982). Synthesis and Kinetics of Ni(Co)3N2 in Liquid Krypton; Indication Of Ni-N2 Bond Energy. J. Chem. Soc.,Chem. Commun., 80, 83-86.
Markwell, R. D., S.Butler, I., Gao, J. P., & Shaver, A. (1993). Near-Infrared Fourier Transform Raman spec. characterization of metal carbonyl in polymers. J. Raman Spectrosc., 24, 423-430.
Miessler, G. L., & Donald, A. T. (2014). Inorganic Chemistry (D. A.T. Ed. 5th Edition ed.). Essex: Prentice Hall. 102-150.
Molvinger, K., Childs, G. I., Jobling, M., Roper, M., George, M. W., & M. Poliakoff. (2000). IR Evidence for the Generation of (C5H5)Mn(CO)2(N2O) in Near-Critical N2O at Room Temperature and polyethylene Matrices at Low Temperature. Chem. Letts., 1260-1261.
Murphy, T. S. (2015). Time-Resolved Spectroscopic Studies of Reactive Intermediates. (PhD Thesis). University of Nottingham, Nottingham. (31288).
Murphy, T. S. (2015). Time-Resolved Spectroscopic Studies of Reactive Intermediates. (PhD). University of Nottingham.
Parker, D. J., & Stiddard, M. H. B. (1968). Vibrational and Electronic Spectra of Transition-metal Carbonyl Complexes. Part V.l Solvent Effects on the Infrared Spectra of the Complexes (C5H5)Mn(CO)3 and (C6Me6)Cr(CO)3. Inorg. Phys. Theor., A, 2263-2264.
Perutz, R. N., & Hall, C. (1996). Transition Metal Alkane Complexes. Chem. Rev., 96, 3125-3146.
Perutz, R. N., & Turner, J. J. (1975). Photochemistry of the Group 6 Hexacarbonyls in Low Temperature Matrices. VI. Tetracarbonylmolybdenum and Tricarbonylmolybdenum. J. Am. Chem. Soc., 97(17), 4800-4804.
Simpson, M. B., Poliakoff, M., Turner, J. J., Maier, W. B., & McLaughlin, J. G. (1983). [Cr(CO)5Xe] in Solution the First Spectroscopic Evidence. J. Chem. Soc., Chem. Commun., 1355-1357.
Smith, J. A., George, M. W., & Kelly, J. M. (2011). Transient spectroscopy of dipyridophenazine metal complexes which undergo photo-induced electron transfer with DNA. Coord. Chem. Rev., 255(21-22), 2666-2675.
Sun, X. Z., Grills, D. C., Nikiforov, S. M., Poliakoff, M., & George, M. W. (1997). Remarkable Stability of CpRe(CO)2L (L = n-Heptane, Xe and Kr): A time resolved infrared spectroscopic study of CpRe(CO)3 in conventional and supercritical fluid solution. J. Am. Chem. Soc., 119, 7521-7525.
Sun, X. Z. N., S. M. Yang, J. Colley, C. S. and George, M. W. (2002). Nanosecond Time-Resolved Step-Scan FT-IR Spectroscopy in Conventional and Supercritical Solvent Using a Four Window Infrared Cell. Appl. Spectrosc., 56(1).
Torres, O., Calladine, J. A., Duckett, S. B., George, M. W., & Perutz, R. N. (2015). Detection of sigma-alkane complexes of manganese by NMR and IR spectroscopy in solution: (η5-C5H5)Mn(CO)2(ethane) and (η5-C5H5)Mn(CO)2(isopentane). Chem. Sci., 6(1), 418-424. Retrieved from http://www.ncbi.nlm.nih.gov/pubmed/28936300
Yang, J. (2003). Time Resolved Infra-Red Spectroscopy of Transient Species in Conventional and Supercritical Fluid Solutions. (PhD Thesis). University of Nottingham, Nottingham. pp. 70.
Yang, J., N’Guessan, B. R., Dedieu, A., Grills, D. C., Sun, X. Z., & George, M. W. (2009). Experimental and Theoretical Investigation into the Formation and reactivity M(Cp)2(CO)2 (M=Mn or Re) in liquid and supercritical CO2 and the effect of different CO2 Coordinatio Modes on Reaction Rates with CO, H2 and N2. Organomets., 28(11), 3113-3122.
Zhou, M., Andrews, L., & Bauschlicher, C. W. (2001). Spectroscopic and Theoretical Investigations of Vibrational Frequencies in Binary Unsaturated Transition-Metal Carbonyl Cations, Neutrals, and Anions. Chem. Rev., 101, 1931-1961.
Downloads
Published
Issue
Section
License
Copyright (c) 2025 Gadau Journal of Pure and Allied Sciences

This work is licensed under a Creative Commons Attribution 4.0 International License.
