Organometallics
ARTICLE
(11) For DMSO as monodentate ligand see: (a) Dorta, R.; Rozen-
berg, H.; Shimon, L. J. W.; Milstein, D. Chem.—Eur. J. 2003, 9, 5237. For
bidentate ligand see: (b) Evans, D. R.; Huang, M.; Seganish, W. M.;
Fettinger, J. C.; Williams, T. L. Inorg. Chem. Commun. 2003, 6, 462.
(c) Cartwright, P. S. C.; Gillard, R. D.; Sillanpaa, E. R. J.; Valkonen, J.
Tetrahedron 1988, 7, 2143.
171, 85. (c) Carvalho, C. C.; Francisco, R. H. P.; Gambardella, M. T. P.;
De Souza, G. F.; Filgueiras, C. A. L. Acta Crystallogr., Sect. C 1996,
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(12) Generally, O-bonding in sulfoxides results in small downfield
chemical shifts of the R-protons (<0.5 ppm), while larger downfield
chemical shifts (1 ppm) are seen for coordination through the S-atom.
This trend is observed for the β- and γ-protons, although the extent of
these effects decreases as the protons become further removed from the
S-atom; see refs 14a and 15d and reference therein.
(29) Grinberg, A. A.; Gel’fma, M. I.; Kiseleva, N. V. Russ. J. Inorg.
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(32) These isomers are often designated as exo and endo when there
is an obvious reference point out of the plane of the square-planar metal
moiety; see: (a) Steinhagen, H.; Reggelin, M.; Helmchen, G. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2108. This description, however, is
ambiguous for a planar PdXY set or in cases where a reference point is
not clear. One might view this as a case of planar chirality; however, a
nomenclature based on axial chirality was suggested by Hayashi:(b)
Hayashi, T.; Kawatsura, M.; Uozumi, Y. J. Am. Chem. Soc. 1998,
120, 1681. This can be awkward when dealing with “axial chirality” of
both the ligand and the metal. Faller et al. consider the Pd system as one
would a chiral pyramidal phosphorus atom, considering the allyl as an
18-electron pseudoatom placed at the centroid of the allyl:(c) Faller,
J. W.; Sarantopoulos, N. Organometallics 2004, 23, 2008.
(33) (a) Albert, J.; Bosque, R.; Cadena, J. M.; Delgado, S.; Granell, J.;
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(13) 1H NMR (CDCl3) of the free ligand (R)-1a for both t-Bu and
methylene proton are 0.93, 4.46, and 4.60, respectively.
(14) Selected reviews: (a) Kagan, H. B.; Ronnan, B. Rev. Heteroat.
Chem. 1992, 7, 92. For review on DMSO bound to metal see:
(b) Calligaris, M.; Carugo, O. Coord. Chem. Rev. 1996, 153, 83. (c)
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M.; Cavicchio, G.; Crucianelli, M.; Panzei, W.; Colapietro, M.; Cassetta,
A. Organometallics 1999, 18, 555.
(16) Iridium 2a and 2b complexes displayed νS-O bands at 1031 and
1056 cmꢀ1, respectively, more shielded than the corresponding free
ligand at 1074 cmꢀ1, which go to the opposite trend observed for other
sulfoxide groups; see refs 9a, 11b, and 12.
(17) For S- and O-bonded sulfone see: (a) Sykes, A.; Mann, K. R.
J. Am. Chem. Soc. 1988, 110, 8252. (b) Randall, S. L.; Miller, C. A.; Janik,
T. S.; Churchill, M. R.; Atwood, J. D. Organometallics 1994, 13, 141.
(18) Calligaris reported only seven X-ray images of iridium com-
plexes, one Ir(I) and six Ir(III), and all of them are S-bonded to the
metal; see ref 11b. Recently Milstein reported more X-ray structures of
S-bonded complexes and the high difficulty to isolate such an O-Ir(I)
complex with DMSO; see ref 14a. For an S-bonded heterobimetallic
complex see: Sykes, A.; Mann, K. R. J. Am. Chem. Soc. 1988, 110, 8252.
(19) Δδ calculated from the free ligand 1a at 60 ppm.
(34) (a) Mason, R.; Russell, D. R. Chem. Commun. 1996, 26. (b)
Filipuzzi, S.; Pregosin, P. S.; Albinati, A.; Rizzato, S. Organometallics
2006, 25, 5955.
(35) Powell, J.; Shaw, B. L. J. Chem. Soc. (A) 1967, 1839.
(36) For a nice review see: Nishio, M. CrystEngComm 2004, 6, 130.
(37) (a) Kodama, Y.; Nishihata, K.; Nishio, M.; Iitaka, Y. J. Chem.
Soc., Perkin Trans. 2 1976, 1490. (b) Onaka, S.; Furuta, H.; Takagi, S.
Angew. Chem., Int. Ed. Engl. 1993, 32, 87. (c) Jitsukawa, K.; Iwai, K.;
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(38) Suezawa, H.; Yoshida, T.; Umezawa, Y.; Tsuboyama, S.; Nishio,
M. Eur. J. Inorg. Chem. 2002, 3148.
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(40) (a) Review: Okawa, H. Coord. Chem. Rev. 1988, 92, 1. (b)
Sakiyama, H.; Okawa, H.; Matsumoto, N.; Kida, S. J. Chem. Soc., Dalton
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(41) (a) Colquhoun, H. M.; Doughty, S. M.; Stoddart, J. F.; Slawin,
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(42) This short distance is significantly smaller than the relevant van
der Waals radii: Suezawa, H.; Yoshida, T.; Umezawa, Y.; Tsuboyama, S.;
Nishio, M. Eur. J. Inorg. Chem. 2002, 3148.
(20) 31P NMR values for complexes III-(cod), 116.5 ppm, and for
bis-PNSO IV, 69.5 ppm; see ref 6.
(21) For Rh(I) complexes see: (a) Wiester, J. M.; Braunscheig, A:B;
Mirkin, C. A. Inorg. Chem. 2010, 49, 7188. For solvent effects in a
supramolecular system see:(b) Leigh, D. A.; Morales, M. A. F.; Perez,
E. M.; Wong, J. K. Y.; Saiz, C. G.; Slawin, A. M. Z.; Carmichael, A. J.;
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S.; Zerbetto, F. Angew. Chem., Int. Ed. 2005, 44, 3062.
(22) Precedent for this type of structural arrangement exists for Ir P,
S ligands: (a) Malacea, R.; Manoury, E.; Routaboul, L.; Daran, J. C.; Poli,
R.; Dunne, J. P.; Withwood, A. C.; Godard, C.; Duckett, S. B. Eur. J. Inorg.
Chem. 2006, 9, 1803. and P,N ligands:(b) Lo Schiavo, S.; Grassi, M.; De
Munno, G.; Nicolo, F.; Tresoldi, G. Inorg. Chim. Acta 1994, 216, 209. (c)
Tejel, C.; Bravi, R.; Ciriano, M. A.; Oro, L. A.; Bordonaba, M.; Graiff, C.;
Tiripicchio, A.; Burini, A. Organometallics 2000, 19, 3115.
(23) (a) Owens, T. D.; Hollander, F. J.; Oliver, A. G.; Ellman, J. A.
J. Am. Chem. Soc. 2001, 123, 1539. (b) Tsujimoto, T.; Ishihara, J.; Horie,
M.; Murai, A. Synlett 2002, 399. (c) Owens, T. D.; Souers, A. J.; Ellman,
J. A. J. Org. Chem. 2003, 68, 3.
(24) Emokpae, T. A.; Ukwueze, A. C.; Walton, D. R.; Hitchockok,
(43) Scrivanti et al. reported an X-ray structure of cationic palladium
complexes that revealed a CH/π interaction between the anti- allyl
proton and a phenyl-phosphine group; see: Scrivanti, A.; Benetollob, F.;
Venzoc, A.; Bertoldinia, M.; Beghettoa, V.; Matteolia, U. J. Organomet.
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(44) Nishio, M.; Umezawa, Y.; Kazumasa, H.; Tsuboyama, S.;
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P. B. Synth. R. Inorg. Met-Org. Chem. 1986, 16, 387.
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(26) Francisco, R. H. P.; Gambardella, M. T. P.; Rodrigues, A. M. G.
D.; De Souza, G. F.; Filgueiras, C. A. L. Acta Crystallogr., Sect. C 1995, 51,
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(27) (a) Filgueiras, C. A. L.; Holland, P. R.; Johnson, B. F. G.;
Raithby, P. R. Acta Crystallogr., Sect. B 1982, 38, 2684. (b) Zhu, F. C.;
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(45) Different palladium sources were tested and always gave the
same results in THF.
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dx.doi.org/10.1021/om200217j |Organometallics 2011, 30, 3119–3130