Abstract
The new phosphines Ph2PC6H4-4-C≡CR [R=SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-C≡CSiMe3)3 (4) and Ru(C≡CC6H4-4-PPh2)(PPh3)2(η-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-C≡CH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(η-C5H5)]PF6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-C≡C)Ru(PPh3)2(η-C5H5)}3 (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, α=108.656(5)°, β=96.344(5)°, γ=93.523(5)°, V=3658.4(6) Å3, Z=2, R=0.078, Rw=0.105 for 5008 reflections [I>2.00σ(I)].
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
C. B. Gorman (1998). Adv. Mater. 10, 295.
M. A. Hearshaw and J. R. Moss (1999). J. Chem. Soc. Chem. Commun. 1.
F. J. Stoddart and T. Welton (1999). Polyhedron 18, 3575.
C. B. Gorman, B. L. Parkhurst, W. Y. Su, and K.-Y. Chen (1997). J. Am. Chem. Soc. 119, 1141.
E. C. Constable, O. Eich, C. E. Housecroft, and L. A. Johnston (1998). Chem. Commun. 2661.
E. C. Constable, C. E. Housecroft, B. Krattinger, M. Neuburger, and M. Zehnder (1999). Organometallics 18, 2565.
W. Gee, R. A. Shaw, and B. C. Smith (1967). Inorg. Synth. 9, 19.
S. Takahashi, Y. Kuroyama, K. Sonogashira, and N. Hagihara (1980). Synthesis 627.
T. Blackmore, M. I. Bruce, and F. G. A. Stone (1971). J. Chem. Soc. (A) 2376.
M. I. Bruce, C. M. Jensen, and N. L. Jones (1989). Inorg. Synth. 26, 259.
M. I. Bruce, J. G. Matisons, and B. K. Nicholson (1983). J. Organomet. Chem. 247, 321.
P. Coppens (ed.), The Evaluation of Absorption and Extinctions in Single-Crystal Structure Analysis, Crystallographic Computing (Indian Academy of Sciences, Bangalore, 1970).
S. Mackay, C. J. Gilmore, C. Edwards, M. Tremayne, N. Stuart, and K. Shankland, maXus Computer Program for the Solution and Refinement of Crystal Structures (Nonius, The Netherlands; MacScience, Japan; University of Glasgow, Glasgow; 2000).
teXsan: Single Crystal Structure Analysis Package (Molecular Structure Corporation, 3200 Research Forest Drive, The Woodlands, TX, 1997).
P. M. Van Calcar, M. M. Olmstead, and A. L. Balch (1998). Inorg. Chim. Acta 270, 28.
M. I. Bruce and R. C. Wallis (1979). Aust. J. Chem. 32, 1471.
I. R. Whittall, M. G. Humphrey, D. C. R. Hockless, B. W. Skelton, and A. H. White (1995). Organometallics 14, 3970.
I. R. Whittall, M. G. Humphrey, A. Persoons, and S. Houbrechts (1996). Organometallics 15, 1935.
I. R. Whittall, M. P. Cifuentes, M. G. Humphrey, B. Luther-Davies, M. Samoc, S. Houbrechts, A. Persoons, G. A. Heath, and D. C. R. Hockless (1997). J. Organomet. Chem. 549, 127.
M. I. Bruce, G. Shaw, and F. G. A. Stone (1972). J. Chem. Soc. Dalton Trans. 2094.
M. I. Bruce, J. G. Matisons, B. W. Skelton, and A. H. White (1983). J. Chem. Soc. Dalton Trans. 2375.
M. I. Bruce, M. J. Liddell, O. bin Shawkataly, C. A. Hughes, B. W. Skelton, and A. H. White (1988). J. Organomet. Chem. 347, 207.
G. Süss-Fink, I. Godefroy, V. Ferrand, A. Neels, and H. Stoeckli-Evans (1998). J. Chem. Soc. Dalton Trans. 515.
M. I. Bruce, D. C. Kehoe, J. G. Matisons, B. K. Nicholson, P. H. Rieger, and M. L. Williams (1982). J. Chem. Soc. Chem. Commun. 442.
P. Lemoine (1982). Coord. Chem. Rev. 47, 55.
P. Zanello (ed.), Stereochemistry of Organometallic and Inorganic Compounds (Elsevier, Amsterdam, 1990), p. 181.
P. Zanello, S. Aime, and D. Osella (1984). Organometallics 3, 1374.
B. M. Peake, B. H. Robinson, J. Simpson, and D. J. Watson (1974). J. Chem. Soc. Chem. Commun. 945.
J. E. Cyr, J. A. DeGray, D. K. Gosser, E. S. Lee, and P. H. Rieger (1985). Organometallics 4, 950.
A. J. Downard, B. H. Robinson, J. Simpson, and A. M. Bond (1987). J. Organomet. Chem. 320, 363.
J. E. Cyr and P. H. Rieger (1991). Organometallics 10, 2153.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lucas, N.T., Cifuentes, M.P., Nguyen, L.T. et al. Ruthenium Cluster Chemistry with Ph2PC6H4-4-C≡CH. Journal of Cluster Science 12, 201–221 (2001). https://doi.org/10.1023/A:1016683331367
Issue Date:
DOI: https://doi.org/10.1023/A:1016683331367