Platinum derivatives of decafluorophosphorobenzene and decafluoroarsenobenzene. The crystal structure of Pt(PPh3)2 (PC6F5)2

Elmes, Patricia S.; Scudder, Marcia L.; West, Bruce O.

doi:10.1016/s0022-328x(00)80621-x

Cited by 50 publications

(12 citation statements)

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“…It was found that the Tbt and ferrocenyl groups of 2b are oriented in a trans conformation with a torsion angle of 156.6(2)°. The Pt−P(PPh 3 ) bond lengths for 2b (2.2841(12) and 2.3025(12) Å) lie in the range of those for platinum complexes 6 − 8 (2.276−2.349 Å). ,, The Pt−P(PP) bond lengths for 2b were 2.3838(12) Å (Tbt group) and 2.3916(12) Å (Fc group), which are similar to those for complexes 6 − 8 (2.319−2.400 Å). ,, Accordingly, the Pt−P(PPh 3 ) bond lengths were shorter than Pt−P(PP), as in the case of the reported Pt complexes 7 and 8 , , suggesting that the p character of the Pt−P(PP) bond of 2b is higher than those of the Pt−P(PPh 3 ) bonds. The P−P bond length of 2b (2.1549(17) Å), being within the range of those for the reported complexes 6 − 8 (2.140−2.156 Å), ,, is shorter than typical P−P single-bond lengths (ca.…”

Section: Resultssupporting

confidence: 52%

“…Although there have been three reports on the crystal structures of [Pt(η 2 -R 1 PPR 2 )(PPh 3 ) 2 ] (R 1 , R 2 : C 6 F 5 , C 6 F 5 ( 6 ); EtMe 4 CpFe(CO) 2 , Mes* ( 7 ); t -Bu 2 P, t -Bu 2 P ( 8 )) revealed by X-ray crystallographic analysis, the structural features of platinum complexes have not been fully investigated until now. The molecular structure of 2b was determined by X-ray crystallographic analysis (Figure ), and the selected structural parameters are summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

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A Ferrocenyldiphosphene−Platinum Complex: Structural Features and Theoretical Calculations

2008

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Section: Resultssupporting

confidence: 52%

Section: Resultsmentioning

confidence: 99%

A Ferrocenyldiphosphene−Platinum Complex: Structural Features and Theoretical Calculations

2008

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“…appears to be unreliable in view of the wide disparity between the shifts found and the very high frequency shifts established for the diphosphenes with bulky groups R.4-7*11*13 *15 Stabilization of molecules RP=PR with less-bulky substituents R, such as C6F5, 16 Ph," SiMe3,18*19 and even H,20*21 has been achieved by q2-co-ordination to transition metals. Co-ordination obviously leads to kinetic stabilization through the interaction of the pn-pn electrons of RP=PR with the metal acceptor orbitals; whether or not co-ordination also affords thermodynamic stabilization against polymerization is unclear.…”

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confidence: 95%

The nature of the co-ordinate link. Part 11. Synthesis and phosphorus-31 nuclear magnetic resonance spectroscopy of platinum and palladium complexes containing side-bonded (E)-diphenyldiphosphene. X-Ray crystal and molecular structures of [Pd{(E)-PhPPPh}(Ph₂PCH₂CH₂PPh₂)] and [Pd{[(E)-PhPPPh][W(CO)₅]₂}(Ph₂PCH₂CH₂PPh₂)]

Chatt¹,

Hitchcock²,

Pidcock³

et al. 1984

J. Chem. Soc., Dalton Trans.

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The complexes cis-[MC12L2] react with Li,(PhPPPh) to give [M(PhP=PPh)L,] [M = Pd, L2 = 1,2-bis(diphenylphosphanyl)ethane (dppe), (1) ; M = Pt, L2 = dppe or (PPh3)2]. Complex (1) reacts with [W(CO),(thf)] (thf = tetrahydrofuran) to give [Pd{(PhP=PPh) [W(CO),],}(dppe)](2). Complexes were characterized by 31 P-{ H} n.m.r. spectroscopy. X-Ray crystal-structure determinations of complexes (1 ) and (2) reveal nearly identical and planar PdP4 moieties comprising the donor atoms of L2 and q2-[(€)-diphenyldiphosphene] ligands. In (2) the two diphosphene lone pairs co-ordinate to W(CO), groups and the W-P bonds are bent 32" away from the Pd atom. The diphosphene P-P bond in (2) [2.186(6) A] is 0.06 A longer than that in (1) [2.121(4) A], which is similar to that in other diphosphene complexes and is approximately mid-way between the P-P single and double bond lengths. Small values of the coupling constants 1J( PtP) and 2J( PP) involving the diphosphene ligand indicate that the diphosphene uses electrons of low s character in q2-co-ordination.Diorganodiphosphenes RP=PR tend to polymerize to cyclopolyphosphanes such as PhP(PPh)+ because the bond energy per phosphorus atom is smaller in the diphosphene (i.e. half the P=P bond energy) than in the polyphosphane (i.e. the P-P bond energy). Although px-pn bonding between elements X from the second and later rows of the Periodic Table leads to the expected maximum in the X2 bond dissociation energies at Group 5, the ratio of the bond energies per atom in X2 to that in the polymers containing single bond X-X is too small for the diatomic molecules X2 to be thermodynamically stable at 25 "C2 At high temperatures entropy favours the smaller molecules X2, and the n-bonded molecules X2 for most of the Main Group elements have been known for a long time. Recent success in the stabilization at room temperature of molecules RP=PR has been achieved by the use of bulky substituents R. In the (E)-configuration of the diphosphene the interaction between the two R groups is minimized, whereas the number and intensity of the steric interactions tend to be greater in the polymeric forms. With sufficiently bulky substituents R, the doubly-bonded molecules become thermodynamically stable at room temperature, and even when full thermodynamic stabilization is not achieved, the bulky R groups reduce the rate of polymerization or attack by other reagents. The molecules RP'PR have been prepared and studied for R = C6H2But3-2,4,6 and other bulky aryl group^,^-'^ C(Si Me3)3,599*1 9 l 2 N(SiMe3)2,13 and N(SiMe,Bu'),. l 3The early report l4 of the detection of monomeric and dimeric forms of PPh by 31P n.m.r. in melts of PhP(PPh)4 now n l l t 1,2-Bis(diphenylpho~phanyl)ethane[(E)-~~-dipheny~diphosphene]palladium(0) and 1-[1',2'-bis(diphenyIphosphanyl)ethane]- 2,2,2,2,2,3,3,3,3, 3-decacarbonyl-[(E)-CI-diphenyldiphosphene- P( Pd' W')P'( Pd W 3)]-palladium(0)d i tungsten(0) respectively. Supplementary data auailable(No. SUP 23947, 30 pp.): thermal parameters, H-atom co-ordinates, structure factors. See Instruc...

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“…The novel compounds were characterized by elemental analyses and spectroscopic methods (IR, and 13C NMR, and mass spectroscopy). The molecular structure of the diarsene derivative (7j5-C5Me5)(CO)2FeAs[Cr(CO)5]=AsR was established by a single-crystal X-ray diffraction study [Pi space group; Z = 2, a = 1057.0 (4) pm, b = 1246.6 (5) pm, c = 1577.2 (7) pm; a = 88.08 (3)°,…”

mentioning

confidence: 99%

Chemistry of C-trimethylsilyl-substituted main Group heterocarboranes. 5. Reactivity of stannacarboranes toward a tridentate Lewis base, 2,2':6',2''-terpyridine. Synthetic, structural, and bonding studies on the donor-acceptor complex 1-Sn[C15H11N3]-2-[Si(CH3)3]-3-(R)-2,3-C2B4H4 [R = Si(CH3)3 and CH3]

Siriwardane¹,

Maguire²,

Banewicz³

et al. 1989

Organometallics

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Platinum derivatives of decafluorophosphorobenzene and decafluoroarsenobenzene. The crystal structure of Pt(PPh3)2 (PC6F5)2

Cited by 50 publications

References 18 publications

A Ferrocenyldiphosphene−Platinum Complex: Structural Features and Theoretical Calculations

A Ferrocenyldiphosphene−Platinum Complex: Structural Features and Theoretical Calculations

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