Table 6 Selected bond distances (Å) and angles (Њ) for compounds 12
and 14
Spectrometery Service Centre at Swansea is also gratefully
acknowledged.
12 (M = Ru)
14 (M = Rh)
References
M(1)–Cl(1)
M(1)–Cl(2)
M(2)–Cl(3)
M(2)–Cl(4)
M(1)–P(1)
M(2)–P(2)
P(1)–O(1)
2.4130(14)
2.4263(15)
2.4076(14)
2.4327(14)
2.3119(14)
2.3443(14)
1.644(4)
2.191(6)–2.266(6)
2.184(5)–2.278(6)
2.4015(10)
2.4320(9)
2.4163(9)
2.3925(10)
2.2944(11)
2.3136(11)
1.641(2)
2.167(3)–2.241(3)
2.158(3)–2.222(3)
1 For a recent review see: P. Espinet and K. Soulantica, Coord. Chem.
Rev., 1999, 193–195, 499.
2 (a) P. Braunstein, C. Charles, G. Kickelbick and U. Schubert, Chem.
Commun., 1997, 1911; (b) S.-L. Li, T. C. W. Mak and Z.-Z. Zhang,
J. Chem. Soc., Dalton Trans., 1996, 3475; (c) R. P. Schutte, S. J. Rettig,
A. M. Joshi and B. R. James, Inorg. Chem., 1997, 36, 5809; (d) S.-M.
Kuang, F. Xue, Z.-Z. Zhang, W.-M. Xue, C.-M. Che and T. C. W.
Mak, J. Chem. Soc., Dalton Trans., 1997, 3409; (e) W.-H. Chan,
Z.-Z. Zhang, T. C. W. Mak and C.-M. Che, J. Chem. Soc., Dalton
Trans., 1998, 803; (f) J. S. Field, R. J. Haines and C. J. Parry, J. Chem.
Soc., Dalton Trans., 1997, 2843.
3 J. L. Bookham, D. M. Smithies and M. Thornton Pett, J. Chem.
Soc., Dalton Trans., 2000, 975; S. J. Berners-Price, R. J. Bowen,
P. Galettis, P. C. Healy and M. J. McKeage, Coord. Chem. Rev., 1999,
185-186, 823; S. J. Berners-Price, R. J. Bowen, T. W. Hambley and
P. C. Healy, J. Chem. Soc., Dalton Trans., 1999, 1337; N. D. Jones,
K. S. MacFarlane, M. B. Smith, R. P. Schutte, S. J. Rettig and
B. R. James, Inorg. Chem., 1999, 38, 3956; S. J. Berners-Price,
R. J. Bowen, P. J. Harvey, P. C. Healy and G. A. Koutsantonis,
J. Chem. Soc., Dalton Trans., 1998, 1743.
M(1)–C range
M(2)–C range
Cl(1)–M(1)–P(1)
Cl(2)–M(1)–P(1)
Cl(1)–M(1)–Cl(2)
Cl(3)–M(2)–P(2)
Cl(4)–M(2)–P(2)
Cl(3)–M(2)–Cl(4)
M(1)–P(1)–O(1)
91.00(5)
85.39(5)
88.81(5)
83.38(5)
87.20(5)
86.49(5)
113.81(14)
87.89(3)
98.44(4)
88.50(4)
88.23(4)
85.15(3)
92.03(4)
116.93(8)
4 F. A. Cotton, E. V. Dikarev, G. T. Jordan IV, C. A. Murillo and
M. A. Petrukhina, Inorg. Chem., 1998, 37, 4611; S.-M. Kuang,
Z.-Z. Zhang, Q.-G. Wang and T. C. W. Mak, Chem. Commun., 1998,
581.
5 (a) C. Hann, A. Vitagliano, F. Giordano and R. Taube,
Organometallics, 1998, 17, 2060; (b) C. Hann, M. Spiegler, E.
Herdtweck and R. Taube, Eur. J. Inorg. Chem., 1998, 1425; (c) N.
Rahmouni, J. A. Osborn, A. De Cain, J. Fischer and A.
Ezzamarty, Organometallics, 1998, 17, 2470; (d) C. Hann, J. Sieler
and R. Taube, Chem. Ber., 1997, 130, 939; (e) G. Jia, H. M. Lee,
I. D. Williams, C. P. Lau and Y. Chen, Organometallics, 1997, 16,
3941.
6 P. Wehman, R. E. Rülke, V. E. Kaasjager, P. C. J. Kamer, H.
Kooijman, A. L. Spek, C. J. Elsevier, K. Vrieze and P. W. N. M. van
Leeuwen, J. Chem. Soc., Chem. Commun., 1995, 331; R. E. Rülke,
V. E. Kaasjager, P. Wehman, C. J. Elsevier, P. W. N. M. van Leeuwen,
K. Vrieze, J. Fraanje, K. Goubitz and A. L. Spek, Organometallics,
1996, 15, 3022; S.-M. Kuang, Z.-Z. Zhang, Q.-G. Wang and T. C. W.
Mak, J. Chem. Soc., Dalton Trans., 1998, 1115; S.-M. Kuang,
Z.-Z. Zhang, Q.-G. Wang and T. C. W. Mak, J. Chem. Soc., Dalton
Trans., 1998, 2927; W.-H. Chan, K.-K. Cheung, T. C. W. Mak and
C.-M. Che, J. Chem. Soc., Dalton Trans., 1998, 873.
7 M. J. Green, K. J. Cavell and P. G. Edwards, J. Chem. Soc., Dalton
Trans., 2000, 853; Y. Kataoka, Y. Tsuji, O. Matsumoto, M. Ohashi,
T. Yamagata and K.Tani, J. Chem. Soc., Chem. Commun., 1995,
2099; H. Yang, M. Alvarez, N. Lugan and R. Mathieu, J. Chem.
Soc., Chem. Commun., 1995, 1721.
8 Y. Kataoka, M. Imanishi, T. Yamagata and K. Tani, Organo-
metallics, 1999, 18, 3563; T. J. Marder, F. A. Cotton, G. L. Powell, S.
M. Tetrick and R. A. Walton, J. Am. Chem. Soc., 1984, 106, 1323.
9 H. Yang, N. Lugan and R. Mathieu, Organometallics, 1997, 16, 2089.
10 Q. Jiang, D. Van Plew, S. Murtuza and X. Zhang, Tetrahedron Lett.,
1996, 37, 797; S. Stoccoro, G. Chelucci, A. Zucca, M. A. Cinellu,
G. Minghetti and M. Manassero, J. Chem. Soc., Dalton Trans., 1996,
1295; G. He, S.-K. Loh, J. J. Vittal, K. F. Mok and P.-H. Leung,
Organometallics, 1998, 17, 3931.
11 M. C. Bonnet, F. Dahan, A. Ecke, W. Keim, R. P. Schulz and
I. Thatchenko, J. Chem. Soc., Chem. Commun., 1994, 615; D.
Drommi, F. Nicoló, C. G. Arena, G. Bruno, F. Faraone and
R. Gobetto, Inorg. Chim. Acta, 1994, 221, 109; A. Caballero,
F. A. Jalón and B. R. Manzano, Chem. Commun., 1998, 1879;
G. Franciò, R. Scopelliti, C. G. Arena, G. Bruno, D. Drommi and
F. Faraone, Organometallics, 1998, 17, 338.
12 E. Drent, P. Arnoldy and P. H. M. Budzelaar, J. Organomet. Chem.,
1993, 455, 247; E. Drent, P. Arnoldy and P. H. M. Budzelaar,
J. Organomet. Chem., 1994, 475, 57.
13 A. Scruvanti, V. Beghetto, E. Campagna, M. Zanato and U.
Matteoli, Organometallics, 1998, 17, 630.
14 A. Dervisi, P. G. Edwards, P. D. Newman, R. P. Tooze, S. J. Coles
and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1998, 3771;
A. Dervisi, P. G. Edwards, P. D. Newman, R. P. Tooze, S. J. Coles and
M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1999, 1113.
15 C. G. Arena, F. Faraone, M. Lanfranchi, E. Rotondo and A.
Tiripicchio, Inorg. Chem., 1992, 31, 4797; G. De Munno, G. Bruno,
C. G. Arena, D. Drommi and F. Faraone, J. Organomet. Chem.,
1993, 450, 263.
Fig. 7 Crystal structure of 14 (solvent omitted for clarity). Displace-
ment ellipsoids are shown at the 30% probability level.
2.4015(10) and Rh(1)–Cl(2) 2.4320(9) Å; Rh(2)–Cl(3)
2.40163(9) and Rh(2)–Cl(4) 2.3925(20) Å] are similar for both
metal fragments. Likewise the bimetallic ruthenium complex 12
shows similar Ru–Cl distances for both disparate ruthenium()
groups. The P(1)–O(1) bond length [1.641(2) Å] in 14 is similar
to that observed in 12 [1.644(4) Å]. There is also an intra-
molecular N–H ؒ ؒ ؒ Clcoord hydrogen bond [N(2) ؒ ؒ ؒ Cl(4) 3.23,
H(2n) ؒ ؒ ؒ Cl(4) 2.41 Å; N(2)–H(2n) ؒ ؒ ؒ Cl(4) 150Њ in 12;
N(1) ؒ ؒ ؒ Cl(3) 3.15, H(1) ؒ ؒ ؒ Cl(3) 2.48 Å; N(1)–H(1) ؒ ؒ ؒ Cl(3)
136Њ in 14] and a C–H ؒ ؒ ؒ Clcoord intermolecular hydrogen bond
[C(2s) ؒ ؒ ؒ Cl(1) 3.43, H(2s) ؒ ؒ ؒ Cl(1) 2.52 Å; C(2s)–
H(2s) ؒ ؒ ؒ Cl(1) 151Њ in 12; C(1s) ؒ ؒ ؒ Cl(2) 3.57, H(1s) ؒ ؒ ؒ Cl(2)
2.70 Å; C(1s)–H(1s) ؒ ؒ ؒ Cl(2) 166Њ in 14] with a CHCl3 solvate.
In summary, straightforward preparative routes to new
potentially multidentate pyridylphosphines have been
developed. This facile method should bode well for the syn-
thesis of new ligands bearing suitably disposed functionalities.
From our complexation studies, using a range of late
transition-metal precursors, variation of the substituent group
in the 3-position can influence the ligand bonding mode e.g.
P-co-ordination, P,N(pyridyl)-chelation, P,PЈ-chelation or
P,PЈ-bridging. These interesting co-ordination properties may
have useful implications in homogeneous catalysis. Further
studies are currently in progress and will be reported in due
course.
Acknowledgements
We thank the EPSRC and King’s College London for the pro-
vision of the X-ray diffractometer and the Nuffield Foundation
for the provision of computing equipment. The EPSRC Mass
J. Chem. Soc., Dalton Trans., 2000, 2771–2778
2777