Solid state structure and reactivity in solution. 8. Implications of the structure of [1,2-bis(diphenylphosphino)ethane] tetra-carbonylmolybdenum(0) to the chelate effect

Bernal, Ivan; Reisner, G. M.; Dobson, Gerard R.; Dobson, Charles B.

doi:10.1016/s0020-1693(00)84520-x

Cited by 30 publications

(16 citation statements)

References 36 publications

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“…The Mo-C bond trans to the pyridine N atom has a bond length of 1.953 (4)A, quite comparable to the trans Mo--C bond [1.958 (3)A] in the Mo(CO)4(nn) complex (Bruins Slot, Murrall & Welch, 1985). Also, the Mo-C bond trans to the P atom has a bond length of 1.998 (4)A, again quite comparable to the Mo-C bonds [ 1.974 (8) and 1.999 (8) A] trans to the P atoms in the complex Mo(CO)4(pp) (Bernal, Reisner, Dobson & Dobson, 1986).…”

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confidence: 84%

“…As expected, the Mo-C bonds trans to the np ligand are strengthened to a greater extent than those cis. In contrast to the contracted X--Mo--X chelate bond angle of 76.62(7) ° in Mo(CO)4(nn ) (nn=phen-anthroline) (Bruins Slot, Murrall & Welch, 1985) and 80.2 (1) ° in Mo(CO)4(pp) [pp = 1,2-bis(diphenylphosphino)ethane] (Bernal, Reisner, Dobson & Dobson, 1986), the N--Mo-P angle in Mo(CO)4(nP) is 88.4(1) ° -much closer to the ideal octahedral geometry. These differences are primarily a result of increased strain in the five-membered chelate ring in the nn and pp complexes that is much less prevalent in the six-membered np derivative.…”

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confidence: 88%

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Structure of tetracarbonyl[2-(β-diphenylphosphinoethyl)pyridine]molybdenum(0)

Cook¹,

Derveer²,

Houk³

et al. 1988

Acta Crystallogr C

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10011.951 (4) and 1.963 (4) A with the longest value for the Co-N(3) bond. One of the amine protons bonded to N(3) is 2.48 A from chloride C1(2), perhaps contributing to the slightly longer Co-NO) bond length. None of the other coordinated amine nitrogens interacts with other atoms in the crystal structure. Dien N lengths in Co(en)(dien)C12÷ are 1.944 (7), 1.974 (7) and 1.993 (7)/~, giving an average Co--N length for this structure of 1.968 A compared with a value of 1.950 A for Co(bpy)(dien)C12+. The opposite pattern appears in the difference in Co-C1 lengths for the two structures. This bond is longer for the bpy structure with a value of 2.263 (2) A, compared with a value of 2.249 (3)A for zc-Co(en)(dien)C12+. Both values are within the range of other Corn-C1 lengths, however.The crystal structure of the complex consists of stacks of complex cations along the crystallographic c axis. The stacking interactions are created by the parallel orientation of planar bipyridine ligands of adjacent cations. Separations between atoms of adjacent bipyridine ligands are greater than 4 A. With the exception of the contact between the H atom of N(3) and C1(2), there are no interactions between the complex cation and the chloride ions and water molecules of the unit cell. Weak hydrogen bonds appear to exist between the hydrogen of water O(1) and chloride C1(3) and between water molecules 0(2) and 0(3). References

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confidence: 84%

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confidence: 88%

Structure of tetracarbonyl[2-(β-diphenylphosphinoethyl)pyridine]molybdenum(0)

Cook¹,

Derveer²,

Houk³

et al. 1988

Acta Crystallogr C

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“…The PMo-P bite angle of 76.240(13)8 is significantly larger than for the tighter 2 (69.732 (16)8) and is only 2.68 smaller than for the five-membered chelate [(dppe)Mo(CO) 4 ] (dppe = 1,2-bis(diphenylphosphino)ethane). [15] The Mo1ÀP1 and Mo1 À P2 bond lengths of 2.5079(4) and 2.4917(4) , respectively, are in the normal range. [1,16] The steric congestion caused by the methyl group at N1 is also reflected in the seven-membered ring, where the P1ÀN1 bond (1.7144 (13) ) is slightly longer than the P1ÀN2 bond (1.6726 (13) ) and the bond angles around N1 are smaller (P1-N1-C1 114.99(10)8 and P1-N1-C5 117.16(11)8 versus P1-N2-C4 121.49(10)8 and P1-N2-C6 121.21 (11)8).…”

Section: Diphos Basket 18mentioning

confidence: 99%

“…of cis-tetracarbonyl(dimethyl 5,6-dimethyl-7-phenyl-7-phosphabicycloA C H T U N G T R E N N U N G [2.2.1]hepta-2,5-diene-2,3-dicarboxylate)(1-phenyl-2,3,6,7-tetrahydro-1H-phosphepine)molybdenum (15): A mixture of complex 12 (0.500 g, 0.85 mmol) and dimethylacetylene dicarboxylate (2.5 mL, 20 mmol) was stirred at 50 8C for 22 h. Column chromatography over silica gel, starting with pentane as eluent and gradually changing to dichloromethane, gave recovered dimethylacetylene dicarboxylate first, followed by compound 15 (390 mg, 63 %) as a yellow oil. Crystallization from dichloromethane/hexane gave yellow crystals.…”

Section: Synthesismentioning

confidence: 99%

Bidentate Phosphorus Baskets by Intramolecular Phosphinidene Addition

Assema

Ehlers

Kanter

et al. 2006

Chemistry A European J

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Intramolecular phosphinidene addition to the C==C bond of Mo-complexed, seven-membered phosphorus heterocycles affords three novel [(diphos)Mo(CO)(4)] complexes (18-20). The three bidentate phosphorus baskets differ in the composition of the seven-membered ring: one of the phosphorus atoms is flanked by CH(2), NCH(3), or O. The unsaturated tetrahydrophosphepine precursors are synthesized by either ring-closing metathesis (C and N derivatives) or by a cyclization sequence (O derivative). The crystal structures of the nitrogen- (19) and oxygen-containing (20) baskets have relatively small P-Mo-P angles of 76.240(13) degrees and 77.626(12) degrees , respectively, and complex 20 has slightly shortened Mo--P bond lengths.

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“…The crystal structures of some bidentate phosphine derivatives of molybdenum(0) carbonyl, [bis(diphenylphosphino)methane]tetracarbonylmolybdenum(0), Mo(CO)a(dppm) (Cheung, Lai & Mok, 1971), [1,2-bis(diphenylphosphino)ethane]-tetracarbonylmolybdenum(0), Mo(CO)4(dppe) (Bernal, Reisner, Dobson & Dobson, 1986), bis [ 1,3-bis-(diphenylphosphino)propane]dicarbonylmolybdenum(0), Mo(CO)2(dppp)2 (Chow, Wang, Sheu & Peng, 1986), [1,3-bis(diphenylphosphino)pro-pane]tetracarbonylmolybdenum(0), Mo(CO)4(dppp), and[ 1,4-bis(diphenylphosphino)butane]tetracarbonylmolybdenum(0), Mo(CO)4(dppb) (Ueng & Hwang, 1991), have been studied to elucidate the detailed three-dimensional architecture of the molecule, to study the chelate effect for the bidentate phosphine ligand, and to investigate the ring effect by tuning the number of the chelate ring. In order to make a comparison with other bidentate phosphine derivatives, especially with Mo(CO)4(dppe), and as part of a series of studies on bidentate phosphine derivatives of molybdenum carbonyl, the two cis-l,2-bis(diphenylphosphino)ethylene derivatives, Mo(CO)a(cis-vpp) and Mo(CO)2(cis-vpp)2, were synthesized and the crystal structures determined.…”

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confidence: 99%

Structures of [cis-1,2-bis(diphenylphosphino)ethylene]tetracarbonylmolybdenum(0) (1) and bis[cis-1,2-bis(diphenylphosphino)ethylene]dicarbonylmolybdenum(0) (2)

Ueng¹,

Leu²

1991

Acta Crystallogr C

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MANOCHA, MIHICHUK, BARTON AND ROBERTSON 725back donation from the W atom. The comparative shortness of the W--As(2) bond compared to the W--As(l) bond can be explained by consideration of their respective trans ligands. The Br(1) atom trans to the As(2) ligand is not as strong a dr acceptor as is the P atom which is trans to As(I), which results in a greater back donation to As(2) and a shortening of the W--As(2) bond length.The room temperature ~H NMR spectrum in the arsenic methyl region is not consistent with the general geometry shown in Fig. 1. The solution I H NMR (90 MHz) data shows four well resolved peaks at 190 (1)K, which indicates that the structure is static, consistent with the solid state results. However, at 219 (1)K the four peaks coalesce into one peak. The single resonance line becomes very sharp at 298 K indicative of a fast-exchange limiting spectrum. In the related complex (L-L)W(CO)212P-(OCH3)3 (Mihichuk, Giesinger, Robertson & Barton, 1987), four peaks were observed at 216 K, which coalesce into two peaks at 221 K and then to one at 239 K. The reason that the title compound remains fluxional at comparatively lower temperature is not clear, but presumably involves the relative radius of the halogen atoms.We thank the University of Regina for financial support to SM and LM and for the provision of computational facilities. A(Mo Ka) = 0"7093 A, /z = 0.46mm -~, F(000) = 1944, T=298 K, final R = 0.033 for 3040 observed reflections. The two Mo--P lengths for compound (1) are almost the same, but the two Mo--P lengths in the same chelate ring for compound (2) are significantly different. The two * To whom correspondence should be addressed. mutually c/s CO groups in compound (1) have larger Mo--C distances than those in compound (2) owing to the presence of only two stronger ~--acceptor CO ligands in the latter compound. The bite angle, LP--Mo--P, of compound (1) is slightly smaller than that of compound (2).

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Solid state structure and reactivity in solution. 8. Implications of the structure of [1,2-bis(diphenylphosphino)ethane] tetra-carbonylmolybdenum(0) to the chelate effect

Cited by 30 publications

References 36 publications

Structure of tetracarbonyl[2-(β-diphenylphosphinoethyl)pyridine]molybdenum(0)

Structure of tetracarbonyl[2-(β-diphenylphosphinoethyl)pyridine]molybdenum(0)

Bidentate Phosphorus Baskets by Intramolecular Phosphinidene Addition

Structures of [cis-1,2-bis(diphenylphosphino)ethylene]tetracarbonylmolybdenum(0) (1) and bis[cis-1,2-bis(diphenylphosphino)ethylene]dicarbonylmolybdenum(0) (2)

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