1997
DOI: 10.1021/ja963692t
|View full text |Cite
|
Sign up to set email alerts
|

Synthesis, Structural Diversity, Dynamics, and Acidity of the M(II) and M(IV) Complexes [MH3(PR3)4]+ (M = Fe, Ru, Os; R = Me, Et)

Abstract: The syntheses of complexes MH2L4 and their protonated analogues [MH3L4]+ (M = Fe (1), Ru (2), Os (3); R = Me (a), Et (b)) are described. The structures of 1a, 1b, and 3a were determined in X-ray diffraction studies. The solution structures of complexes 1−3 were established by detailed NMR investigations. 1a, 2b, and 3a form equilibrium mixtures of two isomers in solution. The iron (1a) and ruthenium (2b) complexes isomerize between six-coordinate M(II) dihydrogen cis-[MH(H2)L4]+ and seven-coordinate M(IV) trih… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1
1

Citation Types

15
74
0

Year Published

2001
2001
2015
2015

Publication Types

Select...
6
2

Relationship

0
8

Authors

Journals

citations
Cited by 85 publications
(89 citation statements)
references
References 79 publications
15
74
0
Order By: Relevance
“…The phosphorus–iron bonds (see Table 3) of the two equatorial phosphorus atoms [2.2400 Å for Fe–P(3), and 2.2226 Å for Fe–P(4)] are slightly longer than those for the two axial atoms, P(1) and P(2) (2.2188 and 2.2161 Å, respectively). This structure is similar to the reported X‐ray structures of cis ‐[FeH(η 2 ‐H 2 )(PMe 3 ) 4 ]BPh 4 16 and cis ‐[FeH(η 2 ‐H 2 ){P(CH 2 CH 2 PPh 2 ) 3 }]BPh 4 · THF, in which the tripodal polyphosphane P(CH 2 CH 2 PPh 2 ) 3 is coordinated to the metal center 18. The short iron–phosphorus bonds observed in cis ‐[FeH(η 2 ‐H 2 ){P(CH 2 CH 2 PPh 2 ) 3 }] + could be attributed to the geometrical disposition of the polyphosphane.…”
Section: Resultssupporting
confidence: 88%
See 1 more Smart Citation
“…The phosphorus–iron bonds (see Table 3) of the two equatorial phosphorus atoms [2.2400 Å for Fe–P(3), and 2.2226 Å for Fe–P(4)] are slightly longer than those for the two axial atoms, P(1) and P(2) (2.2188 and 2.2161 Å, respectively). This structure is similar to the reported X‐ray structures of cis ‐[FeH(η 2 ‐H 2 )(PMe 3 ) 4 ]BPh 4 16 and cis ‐[FeH(η 2 ‐H 2 ){P(CH 2 CH 2 PPh 2 ) 3 }]BPh 4 · THF, in which the tripodal polyphosphane P(CH 2 CH 2 PPh 2 ) 3 is coordinated to the metal center 18. The short iron–phosphorus bonds observed in cis ‐[FeH(η 2 ‐H 2 ){P(CH 2 CH 2 PPh 2 ) 3 }] + could be attributed to the geometrical disposition of the polyphosphane.…”
Section: Resultssupporting
confidence: 88%
“…A remarkable asymmetry of the bonding in the Fe–(η 2 ‐H 2 ) distances has been observed in the refined model. This asymmetry has been reported for cis ‐[Fe(H)(η 2 ‐H 2 )(PR 3 ) 4 ] + (R = H or Me) from X‐ray and computational results, and it has been described as a weak attractive interaction between the hydrido ligand and the H(b) atom in a cis disposition 16,27. The influence of the neighboring BF 4 – counteranion on the elongation of one iron–hydrogen bond has been discarded, because the interatomic H(a) ··· F (2.905 Å) and H(b) ··· F (3.203 Å) distances are too long; the characteristic fluorine signal associated with the BF 4 – counteranion was observed in the 19 F NMR spectrum, and no hydrogen–fluorine interactions were observed in solution.…”
Section: Resultsmentioning
confidence: 57%
“…The intermediate is a ''trihydrogen'' complex (91,92). Although not isolated, evidence exists for its intermediacy in facile H-atom exchange in ReH 2 (H 2 )(CO)(PR 3 ) 3 (93), which can be exceedingly fast even at Ϫ140°C in hydrido(H 2 ) complexes (94)(95)(96)(97)(98)(99). The barrier for hydrogen exchange in IrClH 2 (H 2 )(P i Pr 3 ) 2 is only 1.5 kcal/mol even in the solid state (95,96).…”
Section: Reactivity Of -Complexes: Acidity and Heterolysis Of X-h Bondsmentioning
confidence: 99%
“…Another remarkable reaction that occurs even in the solid involves incorporation of deuterium into the PMe 3 ligands of [Fe(D 2 )H(PMe 3 ) 4 ] + , which may involve agostic interactions in which associative (r-bond metathesis as in equation 2) or dissociative C-H bond activation occurs [96].…”
Section: Catalysis Of Isotopic Exchange By H 2 Complexesmentioning
confidence: 99%