Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State

Schneider, Jörg J.; Hagen, Jörg von; Czap, Norbert; Mason, Sax A.; Bau, Robert; Ensling, Jürgen; Gütlich, Philipp; Wrackmeyer, Bernd

doi:10.1002/(sici)1521-3765(20000218)6:4<625::aid-chem625>3.3.co;2-9

Cited by 5 publications

(9 citation statements)

References 18 publications

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“…The structure of 11 exhibits a four-membered ring of Fe, Sn, O, Sn atoms with the geometrical parameters Fe–Sn = 2.522(1) Å; Sn–O = 2.124(6) Å; Sn···Sn = 3.162 Å; Sn–Fe–Sn = 77.61(3)°; Fe–Sn–O = 93.1(1)°; and Sn–O–Sn = 96.2(2)°. These parameters are similar to those reported by Schneider et al for (η 6 -C 7 H 8 )Fe(μ-OH)H{Sn[CH(SiMe 3 ) 2 ] 2 } 2 . The geometries at Fe are different for the two complexes, with a classic piano-stool geometry for 11 , in contrast with the trigonal planar arrangement of the Fe hydride complex due to the presence of the CO group in 11 .…”

Section: Resultssupporting

confidence: 86%

“…These parameters are similar to those reported by Schneider et al for (η 6 -C 7 H 8 )Fe(μ-OH)H{Sn[CH(SiMe 3 ) 2 ] 2 } 2 . The geometries at Fe are different for the two complexes, with a classic piano-stool geometry for 11 , in contrast with the trigonal planar arrangement of the Fe hydride complex due to the presence of the CO group in 11 . The Fe–Sn distance of 2.522(1) Å is slightly longer than 2.488(1) Å for stannylene iron complex [(η 5 -C 5 H 5 )Fe(CO)(PNN)(SnMe 2 )]OTf but almost identical with (η 6 -C 7 H 8 )Fe(μ-OH)H{Sn[CH(SiMe 3 ) 2 ] 2 } 2 .…”

Section: Resultssupporting

confidence: 85%

“…The geometries at Fe are different for the two complexes, with a classic piano-stool geometry for 11 , in contrast with the trigonal planar arrangement of the Fe hydride complex due to the presence of the CO group in 11 . The Fe–Sn distance of 2.522(1) Å is slightly longer than 2.488(1) Å for stannylene iron complex [(η 5 -C 5 H 5 )Fe(CO)(PNN)(SnMe 2 )]OTf but almost identical with (η 6 -C 7 H 8 )Fe(μ-OH)H{Sn[CH(SiMe 3 ) 2 ] 2 } 2 . The Fe–Sn distances range from 2.460(4) to 2.673(4) Å for complexes of the type (η 5 -C 5 H 5 )Fe(CO) 2 Fe-SnR 3…”

Section: Resultsmentioning

confidence: 92%

“…Complex 11 is a μ-hydroxyl-stannyl(stannylene)iron complex similar to 3 , 4 , and 8 , further stabilized via H-bonding interaction between the OH group and the pyridyl N of the DMAP, Scheme . A related complex, (η 6 -C 7 H 8 )Fe(μ-OH)H{Sn[CH(SiMe 3 ) 2 ] 2 } 2 , exhibits 119 Sn resonances at 326.0, 347.5, and 371.0 ppm due to the presence of diasteroisomers . The 119 Sn resonance for the base-stabilized stannylene iron complex [(η 5 -C 5 H 5 )Fe(CO)(PNN)(SnMe 2 )]OTf has been reported at 496 ppm…”

Section: Resultsmentioning

confidence: 99%

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Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

2013

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Reacting the silylated ferrate [(η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 ] − Li + , obtained from the reaction of [(η 5 -C 5 H 5 )Fe(CO) 2 SiMe 3 ], FpSiMe 3 , and LDA with ClSn t Bu 2 Sn t Bu 2 Cl, we have synthesized the distannane (η 5 -Me 3 SiC 5 H 4 )Fe-(CO) 2 -Sn t Bu 2 Sn t Bu 2 Cl, 5, together with (η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 -Sn t Bu 2 Cl, 6. Photochemical irradiation of 5 resulted in formation of [(η 5 -Me 3 SiC 5 H 4 )Fe(CO)-(Sn t Bu 2 ) 2 (μ-Cl)], 8, which we have characterized spectroscopically. Treatment of 8 with Bu 4 N + OH − led to the formation of the μ-hydroxyl-stannyl(stannylene) complex, which could be further stabilized, via a H-bonding interaction, with 4-(N,N-dimethylamino)pyridine, DMAP, [(η 5 -Me 3 SiC 5 H 4 )Fe(CO)(Sn t Bu 2 ) 2 -(μ-OH-DMAP)] (11). The crystal structure of 11 is reported together with those of 5, 6, (η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 Sn t Bu 2 OH, 15, and the unusual product (η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 -Sn t Bu 2 -(η 5 -Me 3 SiC 5 H 3 )-Fe(CO) 2 Sn t Bu 2 Cl, 7, obtained from the reaction between FpSiMe 3 and a large excess of LDA after quenching with t Bu 2 SnCl 2 .

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Section: Resultssupporting

confidence: 86%

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

2013

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“…Both values are closely comparable to the related complex [(η 6 -C 7 H 8 ) (μ-OH)(H)Fe{Sn[CH(SiMe 3 ) 2 ] 2 } 2 ]. 47 The yaw angles for (( DIPP C) 2 CH 2 ) in 9 (average 7.0°) confirm the absence of significant strain in the metallacycle. 43,48,49 The Fe-C(carbene) bonds (1.966(5) and 1.970(5) Å) are unremarkable for octahedral Fe II , 50 whilst the B-C bond length (1.647(10) Å) is elongated again indicating steric weakening of the B-C bond.…”

Section: Resultsmentioning

confidence: 95%

Synthesis and solvent dependent reactivity of chelating bis-N-heterocyclic carbene complexes of Fe(II) hydrides

Zlatogorsky

Ingleson

2012

Dalton Trans.

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The synthesis and isolation of low coordinate methylenebis-(N-DIPP-imidazole-2-ylidene)iron((II))hydrides, (((DIPP)C)(2)CH(2))FeH(2-y)I(y) ((DIPP = 2,6-di-isopropylphenyl, y = 1 or 0), was complicated by competitive reactions with solvent, rapid reductive elimination of H(2) and/or dissociation of the bis-N-heterocyclic carbene ligand. Addition of KH to (((DIPP)C)(2)CH(2))FeI(2) in THF/haloalkane mixtures enabled a short lived mono-hydride to be trapped by reaction with CH(2)Cl(2) or cyclo-heptylbromide to form (((DIPP)C)(2)CH(2))FeI(X) (X = Cl or Br, respectively). Toluene coordination stabilises iron-mono hydride complexes as (((DIPP)C)(2)CH(2))Fe(II)H{η(6)-(toluene)} species, which can be isolated in low yield from combination of borohydride salts and (((DIPP)C)(2)CH(2))FeI(2) in toluene, including an imidazole C4 deprotonated carbene-borane, methylene(N-DIPP-imidazole-2-ylidene)(N-DIPP-4-triethyl-borane-imidazole-2-ylidene)](hydrido)(η(6)-toluene)iron. In the absence of toluene, or at short reaction times compounds with empirical formula (((DIPP)C)(2)CH(2))Fe(H)(HB(R)(3))·LiI (R = Et or sec-Bu) that function as a masked Fe((II))-dihydride are isolated. Whilst (((DIPP)C)(2)CH(2))Fe(H)(HB(R)(3))·LiI was stable for days in Et(2)O, more polar solvents (MeCN, THF) led to formation of the carbene borane adducts (((DIPP)C)(2)CH(2))(BR(3))(2). The addition of CO or cyclo-heptylbromide to (((DIPP)C)(2)CH(2))Fe(H)(HB(R)(3))·LiI formed (((DIPP)C)(2)CH(2))Fe(CO)(3) and (((DIPP)C)(2)CH(2))FeBr(2), respectively with BR(3) evolved from both reactions as a by-product.

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Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)

et al. 2011

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The new [Pt(5)(CO)(5){Cl(2)Sn(μ-OR)SnCl(2)}(3)](3-) (R = H, Me, Et, (i)Pr; 1-4) clusters contain trigonal bipyramidal (TBP) Pt(5)(CO)(5) cores, as certified by the X-ray structures of [Na(CH(3)CN)(5)][NBu(4)](2)[1]·2CH(3)CN and [PPh(4)](3)[4]·3CH(3)COCH(3). The TBP geometry, which is rare for group 10 metals, is supported by an unprecedented interpenetration with a nonbonded trigonal prism of tin atoms. By capping all the Pt(3) faces, the Sn(II) lone pairs account for both Sn-Pt and Pt-Pt bonding, as indicated by DFT and topological wave function studies. In the TBP interactions, the metals use their vacant s and p orbitals using the electrons provided by Sn atoms, hence mimicking the electronic picture of main group analogues, which obey the Wade's rule. Other metal TBP clusters with the same total electron count (TEC) of 72 are different because the skeletal bonding is largely contributed by d-d interactions (e.g., [Os(5)(CO)(14)(PR(3))(μ-H)(n)](n-2), n = 0, 1, 2). In 1-4, fully occupied d shells at the Pt(ax) atoms exert a residual nucleophilicity toward the adjacent main group Sn(II) ions permitting their hypervalency through unsual metal donation.

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Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State

Cited by 5 publications

References 18 publications

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Synthesis and solvent dependent reactivity of chelating bis-N-heterocyclic carbene complexes of Fe(II) hydrides

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)

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Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State

Cited by 5 publications

References 18 publications

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η5-Me3SiC5H4)Fe(CO)[(SntBu2)2(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η5-Me3SiC5H4)Fe(CO)[(SntBu2)2(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Synthesis and solvent dependent reactivity of chelating bis-N-heterocyclic carbene complexes of Fe(II) hydrides

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt5(CO)5{Cl2Sn(μ-OR)SnCl2}3]3– (R = H, Me, Et, iPr)

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Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Reactions of an Iron Chlorodistannane with Hydroxide: Isolation and Structural Characterization of {(η⁵-Me₃SiC₅H₄)Fe(CO)[(Sn^tBu₂)₂(μ-OH)]···DMAP}, DMAP = 4-(N,N-Dimethylamino)pyridine, a μ-OH-Stannyl(stannylene)–Iron Complex

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)