Synthesis of the Five-Coordinate Ruthenium (II) Complexes [(PCP) Ru

Removal of chloride from the 16-electron complex (PCP)Ru(CO)(Cl) (PCP = 2,6-(CH2PtBu2)2C6H3) in various solvents allows the observation/isolation of ...
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Inorg. Chem. 2005, 44, 8379−8390

Synthesis of the Five-Coordinate Ruthenium(II) Complexes [(PCP)Ru(CO)(L)][BAr′4] {PCP ) 2,6-(CH2PtBu2)2C6H3, BAr′4 ) 3,5-(CF3)2C6H3, L ) η1-ClCH2Cl, η1-N2, or µ-Cl−Ru(PCP)(CO)}: Reactions with Phenyldiazomethane and Phenylacetylene Jubo Zhang,† Khaldoon A. Barakat,‡ Thomas R. Cundari,‡ T. Brent Gunnoe,*,† Paul D. Boyle,† Jeffrey L. Petersen,§ and Cynthia S. Day| Department of Chemistry, North Carolina State UniVersity, Raleigh, North Carolina 27695-8204, Department of Chemistry, UniVersity of North Texas, Box 305070, Denton, Texas 76203-5070, C. Eugene Bennett Department of Chemistry, West Virginia UniVersity, Morgantown, West Virginia 26506-6045, and Department of Chemistry, Wake Forest UniVersity, Winston Salem, North Carolina 27109-7486 Received June 29, 2005

Reaction of (PCP)Ru(CO)(Cl) (1) with NaBAr′4 yields the bimetallic product [{(PCP)Ru(CO)}2(µ-Cl)][BAr′4] (2). The monomeric five-coordinate complexes [(PCP)Ru(CO)(η1-ClCH2Cl)][BAr′4] (3) and [(PCP)Ru(CO)(η1-N2)][BAr′4] (4) are synthesized upon reaction of (PCP)Ru(CO)(OTf) (6) with NaBAr′4 in CH2Cl2 or C6H5F, respectively. The solid-state structures of 2, 3, and 4 have been determined by X-ray diffraction studies of single crystals. The reaction of 3 with PhCHN2 or PhCtCH affords carbon−carbon coupling products involving the aryl group of the PCP ligand in transformations that likely proceed via the formation of Ru carbene or vinylidene intermediates. Density functional theory and hybrid quantum mechanics/molecular mechanics calculations were performed to investigate the bonding of weak bases to the 14-electron fragment [(PCP)Ru(CO)]+ and the energetics of different isomers of the product carbene and vinylidene complexes.

Introduction Coordinatively and electronically unsaturated divalent ruthenium complexes with 14- or 16-electron counts are of interest as possible intermediates in catalytic processes as well as for the fundamental understanding of structure and bonding.1,2 For example, 16-electron Grubbs-type ruthenium catalysts have been successfully applied to olefin metathesis,3-5 coordinatively unsaturated half-sandwich ruthenium complexes with phosphine, amidinate, or carbene ligands have * To whom correspondence should be addressed. E-mail: [email protected]. † North Carolina State University. ‡ University of North Texas. § West Virginia University. | Wake Forest University. (1) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science: Mill Valley, CA, 1987. (2) Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 2nd ed.; John Wiley and Sons: New York, 1994. (3) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (4) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (5) Grubbs, R. H. Tetrahedron 2004, 60, 7117-7140.

10.1021/ic051074k CCC: $30.25 Published on Web 10/06/2005

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been extensively studied,6-13 and several unsaturated ruthenium complexes have been synthesized to study C-H agostic interactions.14-17 Caulton et al. have conducted systematic studies on the synthesis and reactivity of four-coordinate (6) Nagashima, H.; Kondo, H.; Hayashida, T.; Yamaguchi, Y.; Gondo, M.; Masuda, S.; Miyazaki, K.; Matsubara, K.; Kirchner, K. Coord. Chem. ReV. 2003, 245, 177-190. (7) Aneetha, H.; Jime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P.; Sapunov, V. N.; Schmid, R.; Kirchner, K.; Mereiter, K. Organometallics 2002, 21, 5334-5346. (8) Tenorio, M. J.; Puerta, M. C.; Valerga, P. J. Organomet. Chem. 2000, 609, 161-168. (9) Kolle, U.; Rietmann, C.; Raabe, G. Organometallics 1997, 16, 32733281. (10) Campion, B. K.; Heyn, R. H.; Tilley, T. D. J. Chem. Soc., Chem. Commun. 1988, 278. (11) Johnson, T. J.; Huffman, J. C.; Caulton, K. G. J. Am. Chem. Soc. 1992, 114, 2725-2726. (12) Bickford, C. C.; Johnson, T. J.; Davidson, E. R.; Caulton, K. G. Inorg. Chem. 1994, 33, 1080. (13) Huang, J.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem. Soc. 1999, 121, 2674-2678. (14) Huang, D.; Streib, W. E.; Eisenstein, O.; Caulton, K. G. Angew. Chem., Int. Ed. Engl. 1997, 36, 2004-2006. (15) Tenorio, M. J.; Tenorio, M. A. J.; Puerta, M. C.; Valerga, P. Inorg. Chim. Acta 1997, 259, 77-84.

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Zhang et al. complexes of the type [L2Ru(CO)(R)][BAr′4] (R ) H, Me, or Ph; Ar′ ) 3,5-(CF3)2C6H3; L ) phosphine ligands) as well as their five-coordinate precursors and have extended their studies to systems with the chelating PNP (PNP ) N(SiMe2CH2PR2)2, R ) Cy or tBu) ligands.14,18-23 Our group has been interested in studying the reactivity of coordinatively unsaturated ruthenium complexes with a bulky PCP pincer ligand (PCP ) 2,6-(CH2PtBu2)2C6H3), and we have previously reported the synthesis of the amido complexes (PCP)Ru(CO)(NHR) (R ) H or Ph) and their reactivity with substrates that possess polar as well as nonpolar bonds.24-26 For example, the ruthenium parent amido complex (PCP)Ru(CO)(NH2) has been demonstrated to initiate the activation of dihydrogen as well as the intramolecular activation of C-H bonds.24 The reaction of (PCP)Ru(CO)(PMe3)(NHPh) with organic substrates such as nitriles, carbodiimides, and isocyanates likely proceeds via PMe3 dissociation, coordination of the organic substrate, and intramolecular nucleophilic addition of the amido nitrogen to form azametallacyclobutane complexes.25,26 Herein, we report that efforts to access a four-coordinate ruthenium complex starting from the five-coordinate precursor (PCP)Ru(CO)(Cl) (1) lead to the formation of complexes of the type [(PCP)Ru(CO)(L)]+ {L ) η1-ClCH2Cl, η1-N2, C6H5F, or µ-Cl-Ru(PCP)(CO)}.27 We anticipated that the geometrical restriction of the meridional coordinating tridentate PCP ligand might lead to chemistry that diverges from that of Caulton et al.’s [L2Ru(CO)(R)]+ systems. Reactions of [(PCP)Ru(CO)(ClCH2Cl)]+ with a carbene source or a phenylacetylene yield products that are intermediates for carbene or vinylidene insertion into the Ru aryl bond of the PCP ligand. Computational studies of these systems are also presented and discussed. Results and Discussions Synthesis and Solid-State Structures of [{(PCP)Ru(CO)}2(µ-Cl)][BAr′4] (2), [(PCP)Ru(CO)(η1-ClCH2Cl)][BAr′4] (3), and [(PCP)Ru(CO)(η1-N2)][BAr′4] (4). The air stable 16-electron compound 1 has been synthesized and structurally characterized by Gusev and co-workers.27 Chlo(16) Baratta, W.; Herdtweck, E.; Rigo, P. Angew. Chem., Int. Ed. 1999, 38, 1629-1631. (17) Tenorio, M. J.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc. 2000, 122, 11230-11231. (18) Huang, D.; Streib, W. E.; Bollinger, J. C.; Caulton, K. G.; Winter, R. F.; Scheiring, T. J. Am. Chem. Soc. 1999, 121, 8087-8097. (19) Huang, D.; Bollinger, J. C.; Streib, W. E.; Folting, K.; Young, V., Jr.; Eisenstein, O.; Caulton, K. G. Organometallics 2000, 19, 2281-2290. (20) Watson, L. A.; Coalter, J. N., III; Ozerov, O. V.; Pink, M.; Huffman, J. C.; Caulton, K. G. New J. Chem. 2003, 263. (21) Watson, L. A.; Ozerov, O. V.; Pink, M.; Caulton, K. G. J. Am. Chem. Soc. 2003, 125, 8426-8427. (22) Walstrom, A. N.; Watson, L. A.; Pink, M.; Caulton, K. G. Organometallics 2004, 23, 4814-4816. (23) Walstrom, A.; Pink, M.; Yang, X.; Tomaszewski, J.; Baik, M.-H.; Caulton, K. G. J. Am. Chem. Soc. 2005, 127, 5330-5331. (24) Conner, D.; Jayaprakash, K. N.; Cundari, T. R.; Gunnoe, T. B. Organometallics 2004, 23, 2724-2733. (25) Zhang, J.; Gunnoe, T. B.; Boyle, P. D. Organometallics 2004, 23, 3094-3097. (26) Zhang, J.; Gunnoe, T. B.; Petersen, J. L. Inorg. Chem. 2005, 44, 28952907. (27) Gusev, D. G.; Madott, M.; Dolgushin, F. M.; Lyssenko, K. A.; Antipin, M. Y. Organometallics 2000, 19, 1734-1739.

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ride abstraction from 1 could afford a four-coordinate ruthenium center; however, the reaction of complex 1 with 1 equiv of NaBAr′4 in CH2Cl2 results in the formation of a mixture of two products that could not be separated. Given the possibility of formation of a binuclear species with a bridging chloride ligand, we reacted complex 1 with 0.5 equiv of NaBAr′4. Clean isolation of the complex [{(PCP)Ru(CO)}2(µ-Cl)][BAr′4] (2) in 80% yield was obtained after workup (eq 1). Complex 2 is air sensitive, as indicated by

slow decomposition of a CD2Cl2 solution of 2 in air. Salient features of the 1H NMR spectrum of 2 include overlapping multiplets in the region 1.74-0.85 ppm due to the PCP tertbutyl groups, as compared to two virtual triplets for 1.27 Also, doublets at 74.1 and 68.9 ppm (JPP ) 228 Hz) are observed in the 31P NMR spectrum of 2, while IR spectroscopy reveals νCO ) 1939 cm-1. Further reaction of 2 with NaBAr′4 or reaction of 1 with excess NaBAr′4 results in a mixture of complex 2 and a second product; however, the second product could not be isolated cleanly. A single crystal of 2 grown from a methylene chloride solution layered with pentane was selected for an X-ray diffraction study. A limited resolution data set revealed the presence of two {(PCP)Ru(CO)} fragments connected with a bridging chloride (Figure 1). The low yield of highresolution data for this compound is presumably due to the presence of disordered CH2Cl2 and pentane solvent molecules of crystallization as well as disordered CF3 groups of the anion. Nonetheless, the X-ray data are consistent with the assigned structure based on spectroscopic and elemental analysis data. As reported previously, the treatment of complex 1 with excess trimethylsilyltriflate (TMSOTf) affords (PCP)Ru(CO)(OTf) (OTf ) η1-OSO2CF3) (6).25 When 1 equiv of NaBAr′4 was added to a CH2Cl2 solution of 6, the CO

Figure 1. ORTEP diagram (30% probability) of [{(PCP)Ru(CO)}2(µ-Cl)][BAr′4] (2) (hydrogen atoms and the BAr′4 counterion have been omitted for clarity).

Synthesis of FiWe-Coordinate Ru(II) Complexes Scheme 1. Reaction of (PCP)Ru(CO)(OTf) (6) with NaBAr′4 in CH2Cl2 or in C6H5Fa

a Complex 5 has not been fully characterized, and its identity is suggested based on evidence from IR spectroscopy and computational studies.

absorption changed from 1941 to 1964 cm-1 within 30 min, as determined by IR spectroscopy. A highly air sensitive product that turns black immediately upon exposure to air can be isolated after workup. Characterization using 1H, 31P, and 19F NMR and IR spectroscopy as well as X-ray crystallography revealed the complex as [(PCP)Ru(CO)(η1ClCH2Cl)][BAr′4] (3) (Scheme 1). Instead of formation of a four-coordinate complex, a molecule of CH2Cl2 coordinates to the ruthenium center through a single chlorine atom. A singlet at 5.35 ppm in the 1 H NMR spectrum of 3 in CD2Cl2 is most likely due to free CH2Cl2 as a result of rapid exchange of coordinated CH2Cl2 with CD2Cl2. The PCP ligand yields two virtual triplets at 1.50 and 1.11 ppm (N ) 15 Hz) in the 1H NMR spectrum and a broad singlet at 71.0 ppm in the 31P NMR spectrum of 3. Although the fragment [(PCP)Ru(CO)]+ has two available coordination sites, the X-ray structural analysis of 3 confirmed the presence of a monohapto coordinated η1-CH2Cl2 ligand (Figure 2). The bond length of Ru1-Cl1s (2.614(1) Å) is longer than the Ru-Cl bond distance in 1 (2.420(1) Å). The C-Cl (bound) distance is 1.791(5) Å while the C-Cl (unbound) distance is 1.695(5) Å. The Cl-C-Cl bond angle is 115.5(2)° with the unbound Cl oriented toward the carbonyl group. One agostic interaction is indicated based on the short Ru/Cagostic distance (Ru1‚‚‚C23, 2.85(1) Å), and the bond angle Ru1-P2-C22 (100.9(1)°) is significantly smaller than the other three tert-butyl group bond angles (113.4(1)°, 121.8(1)°, and 127.8(1)°). Previously, Caulton et al. observed double agostic interactions for the complex [Ru(Ph)(CO)(PtBu2Me)2][BAr′4] with Ru/Cagostic bond lengths of 2.87 and 2.88 Å and Ru-P-C bond angles of 98.1° and 96.6°.14 An agostic interaction has been observed in the solidstate structure of [(PCP)Ru(CO)2]+ with a reported Ru‚‚‚HC distance of 2.19(6) Å.28 Although both bidentate and monodentate CH2Cl2 ligands have been reported, examples of structurally characterized complexes with CH2Cl2 ligands are relatively rare.19,29-36 For example, the synthesis and solid(28) van der Boom, M. E.; Iron, M. A.; Atasoylu, O.; Shimon, L. J. W.; Rozenberg, H.; Ben-David, Y.; Konstantinovski, L.; Martin, J. M. L.; Milstein, D. Inorg. Chim. Acta 2004, 357, 1854-1864.

Figure 2. ORTEP diagram (30% probability) of [(PCP)Ru(CO)(η1ClCH2Cl)][BAr′4] (3) (hydrogen atoms, except the two on CH2Cl2, and the BAr′4 counterion have been omitted for clarity). Selected bond lengths (Å) and bond angles (deg): Ru1-Cl1s, 2.614(1); Ru1-C2, 2.053(3); C1sCl1s, 1.791(5); C1s-Cl2s, 1.695(5); Cl1s-C1s-Cl2s, 115.5(2); Ru1Cl1s-C1s, 123.1(2); C2-Ru1-Cl1s, 170.7(2); Ru1-P2-C22, 100.9(1); Ru1-P2-C18, 127.8(1); Ru1-P1-C14, 113.4(1); Ru1-P1-C10, 121.8(1); P1-Ru1-P2, 161.5(1).

state structures of [RuH(CO)(PMetBu2)2(η2-CH2Cl2)][BAr′4], [Cp*Ir(Me)(η1-ClCH2Cl)][BAr′4], [trans-(PiPr3)2Pt(H)(η1ClCH2Cl)][BAr′4], and [cis-Re(CO)4(PPh3)(η1-ClCH2Cl)][BAr′4] have been reported (Cp* ) pentamethylcyclopentadienyl).19,30-32 The ruthenium hydride complex [Ru(H)(η2CH2Cl2)(CO)(PtBu2Me)2][BAr′4] with an η2-coordinated CH2Cl2 has been reported, while the closely related ruthenium phenyl compound [Ru(Ph)(CO)(PtBu2Me)][BAr′4] could be crystallized from a CH2Cl2 solution without evidence of CH2Cl2 coordination.14,19 Complexes with other chloroalkanes or chlorobenzene ligands have been reported.33,37-39 To exclude the possibility of CH2Cl2 coordination, 1 equiv of NaBAr′4 was reacted with 6 in fluorobenzene. IR spectroscopy revealed two CO absorptions at 1987 cm-1 (major) and 1953 cm-1 (minor). In addition, an absorption at 2249 cm-1 was observed and assigned to coordinated dinitrogen. Free dinitrogen exhibits an absorption at 2331 cm-1 (Raman).1,2 Purging the solution with argon results in the transformation to a solution with a single CO absorption at 1953 cm-1 and the disappearance of absorptions previously (29) Kulawiec, R. J.; Crabtree, R. H. Coord. Chem. ReV. 1990, 99, 89. (30) Arndtsen, B. A.; Bergman, R. G. Science 1995, 270, 1970-1972. (31) Butts, M. D.; Scott, B. L.; Kubas, G. J. J. Am. Chem. Soc. 1996, 118, 11831-11843. (32) Huhmann-Vincent, J.; Scott, B. L.; Kubas, G. J. J. Am. Chem. Soc. 1998, 120, 6808-6809. (33) Peng, T.-S.; Winter, C. H.; Gladysz, J. A. Inorg. Chem. 1994, 33, 2534-2542. (34) Colsman, M. R.; Newbound, T. D.; Marshall, L. J.; Noirot, M. D.; Miller, M. M.; Wulfsberg, G. P.; Frye, J. S.; Anderson, O. P.; Strauss, S. H. J. Am. Chem. Soc. 1990, 112, 2349-2362. (35) Newbound, T. D.; Colsman, M. R.; Miller, M. M.; Wulfsberg, G. P.; Anderson, O. P.; Strauss, S. H. J. Am. Chem. Soc. 1989, 111, 37623764. (36) Bown, M.; Waters, J. M. J. Am. Chem. Soc. 1990, 112, 2442-2443. (37) Van Seggen, D. M.; Anderson, O. P.; Strauss, S. H. Inorg. Chem. 1992, 31, 2987-2990. (38) Wu, F.; Dash, A. K.; Jordan, R. F. J. Am. Chem. Soc. 2004, 126, 15360-15361. (39) Ben-Ari, E.; Gandelman, M.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D. J. Am. Chem. Soc. 2003, 125, 4714-4715.

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observed at 1987 and 2249 . However, this change is reversible, as purging the resultant solution with dinitrogen leads to observation of the three original absorptions at 1987, 1953, and 2249 cm-1. These results suggest an equilibrium between a five-coordinate dinitrogen complex, [(PCP)Ru(CO)(N2)][BAr′4] (4), with a labile N2 ligand, and a second complex that is likely either the four-coordinate complex [(PCP)Ru(CO)][BAr′4] or the fluorobenzene complex [(PCP)Ru(CO)(FC6H5)][BAr′4]. Repeated attempts to grow crystals and perform an X-ray diffraction study of this complex have failed; however, on the basis of IR evidence, we propose that the coordination of fluorobenzene is more likely, though not definitively shown, than the formation of a fourcoordinate system. For example, the series of Ru(II) systems Ru(Ph)(CO)(Cl)L2, Ru(Ph)(CO)(OTf)L2, and [Ru(Ph)(CO)L2][BAr′4] (where L ) PtBu2Me and the latter complex is a four-coordinate system with two agostic interactions) exhibits CO absorptions (IR spectroscopy) at 1902, 1921, and 1958 cm-1, respectively.14,18,19 The series of systems (PCP)Ru(CO)(Cl), (PCP)Ru(CO)(OTf), and the uncharacterized complex has CO absorptions at 1919, 1941, and 1953 cm-1. The conversion of the (PCP)Ru-Cl complex to the (PCP)RuOTf complex results in an increase in the CO stretching frequency of 22 cm-1, while the conversion of the Ru(Ph)(CO)(Cl)L2 complex to the corresponding triflate complex, Ru(Ph)(CO)(OTf)L2, results in an increase in the CO stretching frequency of 19 cm-1. Thus, for the two types of Ru systems, conversion of a Ru-Cl bond to a Ru-OTf bond yields quite similar changes in the energy of the CO stretches. The conversion of the five-coordinate complex Ru(Ph)(CO)(OTf)L2 to the four-coordinate complex [Ru(CO)(Ph)L2][BAr′4] increases the CO absorption energy by 37 cm-1, while the transformation of (PCP)Ru(CO)(OTf) to complex 5 results in an increase of the CO absorption energy of only 12 cm-1. Thus, without confirmation by X-ray crystallography, we assign the identity of this system as [(PCP)Ru(CO)(FC6H5)][BAr′4] (5) (Scheme 1), and calculations are consistent with the notion that the coordination of fluorobenzene is favorable to a four-coordinate complex (see below). The formation of a binuclear species with a bridging dinitrogen ligand is another possibility for complex 5; however, the reaction of (PCP)Ru(CO)(OTf) with NaBAr′4 in C6H5F under argon produces complex 5 (as indicated by IR spectroscopy) and provides evidence against a complex that possesses a bridging dinitrogen moiety. When an excess of CH2Cl2 is added to the solution of 4 and 5, conversion to complex 3 is observed, as indicated by a single CO absorption at 1964 cm-1 in the IR spectrum (eq 2).

The identity of [(PCP)Ru(CO)(η1-N2)][BAr′4] (4) has been confirmed by a single-crystal X-ray diffraction study (Figure 3). Similar to the case of complex 3, one agostic interaction

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Figure 3. ORTEP diagram (30% probability) of [(PCP)Ru(CO)(η1-N2)][BAr′4] (4) (hydrogen atoms and the BAr′4 counterion have been omitted for clarity). Selected bond lengths (Å) and bond angles (deg): Ru1-C2, 2.059(2); Ru1-N1, 2.132(1); N1-N2, 1.069(3); Ru1-C1, 1.809(2); C1O1, 1.148(2); N1-N2, 1.069(3); C2-Ru1-N1, 175.7(1); Ru1-N1-N2, 179.1(2); Ru1-P2-C22, 101.2(1); P1-Ru1-P2, 162.8(1).

is indicated by a short Ru/Cagostic distance (Ru1‚‚‚C23, 2.89 Å) and a small Ru-P-C bond angle (Ru1-P2-C22, 101.2(1)°). A Ru-N bond length of 2.132(1) Å and a linear Ru-N-N bond angle (179.1(2)°) are observed. The N1N2 bond length (1.069(3) Å) is shorter than that in free N2 (1.0975 Å);40 however, correction of selected bond lengths for rigid body motion and riding effects resulted in a corrected N1-N2 bond length of 1.098 Å, which is indistinguishable from the N-N bond length in free dinitrogen (see the Supporting Information for details). A rhodium dinitrogen complex with an “aliphatic” PCP ligand, Rh(η1-N2){η1-CH3C(CH2CH2PtBu2)2}, has been reported with a short N-N bond length of 0.963(14) Å.41 Other complexes with short N-N bond lengths for dinitrogen ligands include trans-ReCl(N2)(PMe2Ph)2 (1.055(30) Å), trans-RhCl(N2)(PiPr3)2 (0.958(5) Å), and trans-RhH(N2)(PPhtBu2)2 (1.074(7) Å) with the bond contraction due to disorder.42-44 For complex 4, the atom N2 displays a relatively high atomic displacement amplitude perpendicular to the N-N bond vector. However, there was no evidence of a multiple site orientational or compositional disorder in the final difference Fourier map (see the Supporting Information). The Ru-N bond distance of 4, 2.132(1) Å, is longer than the bond distances of related Ru-dinitrogen complexes. For example, Ru(II) systems with bisphosphine “pincer” ligands with η1-N2 ligands have Ru-N bond distances in the range of 1.965(4)-2.014(2) Å.45-47 For all of these systems, the observed dinitrogen stretching frequencies in (40) Fryzuk, M. D.; Johnson, S. A. Coord. Chem. ReV. 2000, 200-202, 379-409. (41) Vigalok, A.; Kraatz, H.-B.; Konstantinovski, L.; Milstein, D. Chem.s Eur. J. 1997, 3, 253-260. (42) Ibers, J. A.; Mingos, D. M. P. Inorg. Chem. 1971, 10, 1035-1042. (43) Hoffman, P. R.; Yoshida, T.; Okano, T.; Otsuka, S.; Ibers, J. A. Inorg. Chem. 1976, 15, 2462-2466. (44) Thorn, D. L.; Tulip, T. H.; Ibers, J. A. J. Chem. Soc., Dalton Trans. 1979, 2022-2025. (45) Gusev, D. G.; Fontaine, F.-G.; Lough, A. J.; Zargarian, D. Angew. Chem., Int. Ed. 2003, 42, 216-219. (46) Gusev, D. G.; Lough, A. J. Organometallics 2002, 21, 5091-5099. (47) Amoroso, D.; Jabri, A.; Yap, G. P. A.; Gusev, D. G.; dos Santos, E. N.; Fogg, D. E. Organometallics 2004, 23, 4047-4054.

Synthesis of FiWe-Coordinate Ru(II) Complexes Table 1. Selected Crystallographic Data and Collection Parameters for Complexes 2, 3, 4, 7, and 8 complex

[{(PCP)Ru(CO)}2(µCl)][BAr′4] (2)

[(PCP)Ru(CO)(η1CH2Cl2)][BAr′4] (3)

empirical C93H124B Cl3 F24O2 P4Ru2 C58H57BCl2F24OP2Ru formula formula wt 2173.10 1470.77 cryst syst monoclinic triclinic space group P21/c P1h a, Å 12.970(4) 13.4350(4) b, Å 27.644(7) 13.5298(4) c, Å 29.174(8) 17.9662(5) R, deg 98.7273(11) β, deg 96.932(5) 106.3306(10) γ, deg 94.8176(11) V, Å3 10383(5) 3069.99(15) Z 4 2 Dcalcd, g/cm3 1.390 1.591 R, Rwa 0.066, 0.114 0.049, 0.060 GOF 0.699 1.84 a See the Supporting Information for definitions of R and R . w

[(PCP)Ru(CO)(η1N2)][BAr′4] (4)

[(PCP-CHPh)Ru(CO)] [BAr′4] (7)

[(PCP-CCHPh)Ru(CO)] [BAr′4] (8)

C66H62.50BF25.50N2OP2Ru

C64H61BF24P2ORu

C66H63BCl2F24OP2Ru

1558.01 triclinic P1h 12.3183(6) 12.6860(6) 22.7533(12) 102.535(3) 94.787(3) 91.770(3) 3454.4(3) 2 1.498 0.051, 0.058 1.92

1475.95 triclinic P1h 12.794(1) 15.129(1) 18.119(1) 73.841(1) 79.979(1) 89.871(1) 3313.1(4) 2 1.480 0.062, 0.164 1.023

1572.88 orthorhombic Pna21 24.883(3) 15.962(2) 17.930(2)

the IR spectra are