Abstract
Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes [PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of [PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave [PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave [Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with [PtX2{Ph2PCH(Me)PPh2}] gave [Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and [Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with [Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave [Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes [PtMe2(dpmMe)] or [Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph2PCH(Me)PPh2]. Treatment of [Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of [Ir(CO)(dpmMe)2]Cl with [Cu(C≡CPh)2], [AgCl(PPh3)] or [AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)2]Cl in CHCl3 gave [RhHCl(dpmMe)2]Cl. Recrystallization of [Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave [RhO2(dpmMe)2]BPh4. Treatment of [Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and [Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
Similar content being viewed by others
References
R. J. Puddephatt, Chem. Soc. Rev., 12, 99 (1983).
J. A. Connor, J. P. Day, E. M. Jones and G. K. McEwen, J. Chem. Soc., Dalton Trans., 347 (1975).
M. P. Brown, R. J. Puddephatt, M. Rashidi and K. R. Seddon, J. Chem. Soc., Dalton Trans., 951 (1977).
D. M. McEwan, P. G. Pringle and B. L. Shaw, J. Chem. Soc., Chem. Commun., 859 (1982).
C. A. McAulife and W. Levason, Phosphine Arsine and Stilbine Complexes of Transition Elements, Elsevier, Amsterdam, 1979.
G. J. Palenik, M. Mathew, W. L. Steffen and G. Beran, J. Am. Chem. Soc., 97, 1059 (1975).
W. L. Steffen and G. J. Palenik, Inorg. Chem., 15, 2432 (1976).
E. Ercolani, J. V. Quagliano and L. M. Vallarino, Inorg. Chim. Acta, 7, 413 (1973).
T. G. Appleton, M. A. Bennett and B. Tomkins, J. Chem. Soc., Dalton Trans., 439 (1976).
S. Hietkamp, D. J. Stufkens and K. Vrieze, J. Organomet. Chem., 169, 107 (1979).
M. D. Fryzuk, Inorg. Chim. Acta, 54, L265 (1981).
A. F. M. J. van der Plog and G. van Koten, Inorg. Chim. Acta, 51, 225 (1981).
S. A. AL-Jibori, Transition Met. Chem., 20, 523 (1995).
W. Hewertson and H. R. Watson, J. Chem. Soc., 1490 (1962).
S. O. Grim and E. D. Walton, Inorg. Chem., 19, 1982 (1980).
R. Appel, K. Giesle and H. F. Scholer, Chem. Ber., 112, 648 (1979).
J. X. McDermott, M. E. Wilson and G. M. Whitesides, J. Am. Chem. Soc., 98, 6529 (1976).
D. J. Peterson, J. Organomet. Chem., 8, 199 (1967).
I. J. Colquhoun, H. C. E. McFarlane and W. McFarlane, J. Chem. Soc., Chem. Commun., 220 (1982).
G. M. Kosolapoff and L. Maier, Organic Phosphorus Compounds, Wiley-Interscience, New York, Vol. 4, 1976.
S. Al-Jibori and B. L. Shaw, Inorg. Chim. Acta, 65, L123 (1982).
P. Pringle and B. L. Shaw, J. Chem. Soc., Chem. Commun., 581 (1982).
S. A. Al-Jibori and B. L. Shaw, J. Chem. Soc., Chem. Commun., 286 (1982).
S. M. Nelson, M. Perks and B. J. Walker, J. Chim. Soc., Perkin 1, 1205 (1976).
P. G. Pringle and B. L. Shaw, J. Chem. Soc., Chem. Commun., 1313 (1982).
J. T. Mague and J. P. Mitchener, Inorg. Chem., 18, 2060 (1979).
S. A. Al-Jibori, C. Crocker, W. S. McDonald and B. L. Shaw, J. Chem. Soc., Dalton Trans., 1572 (1981).
S. A. Al-Jibori and L. J. A-Hayaly, unpublished observations.
J. T. Mague and J. P. Mitchener, Inorg. Chem., 8, 119 (1969).
M. Cowie, J. T. Mague and A. R. Sanger, J. Am. Chem. Soc., 100, 3628 (1978).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Al-Hayaly, L.J. Platinum, iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me, Ph or SiMe3). Transition Metal Chemistry 23, 221–226 (1998). https://doi.org/10.1023/A:1015715623361
Issue Date:
DOI: https://doi.org/10.1023/A:1015715623361