Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count
Identifieur interne : 003367 ( Istex/Corpus ); précédent : 003366; suivant : 003368Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C9R7)2M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of d -electron count
Auteurs : Steve A. Westcott ; Ashok K. Kakkar ; Graham Stringer ; Nicholas J. Taylor ; Todd B. MarderSource :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 1990.
Abstract
The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.
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DOI: 10.1016/0022-328X(90)87268-I
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<front><div type="abstract" xml:lang="en">The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</div>
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<abstract>The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe > Co > Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe > Co > Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</abstract>
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<abstract xml:lang="en"><p>The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</p>
</abstract>
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<revisionDesc><change when="1990-02-13">Received</change>
<change when="1990">Published</change>
</revisionDesc>
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<istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>JOM</jid>
<aid>9087268I</aid>
<ce:pii>0022-328X(90)87268-I</ce:pii>
<ce:doi>10.1016/0022-328X(90)87268-I</ce:doi>
<ce:copyright type="unknown" year="1990"></ce:copyright>
</item-info>
<head><ce:title>Flexible coordination of indenyl ligands in sandwich complexes of transition metals. Molecular structures of [(η-C<ce:inf>9</ce:inf>
R<ce:inf>7</ce:inf>
)<ce:inf>2</ce:inf>
M] (M = Fe, R = H, Me; M = Co, Ni, R = H): Direct measurement of the degree of slip-fold distortion as a function of <ce:italic>d</ce:italic>
-electron count</ce:title>
<ce:author-group><ce:author><ce:given-name>Steve A.</ce:given-name>
<ce:surname>Westcott</ce:surname>
</ce:author>
<ce:author><ce:given-name>Ashok K.</ce:given-name>
<ce:surname>Kakkar</ce:surname>
</ce:author>
<ce:author><ce:given-name>Graham</ce:given-name>
<ce:surname>Stringer</ce:surname>
</ce:author>
<ce:author><ce:given-name>Nicholas J.</ce:given-name>
<ce:surname>Taylor</ce:surname>
<ce:ranking><ce:sup>∗</ce:sup>
</ce:ranking>
</ce:author>
<ce:author><ce:given-name>Todd B.</ce:given-name>
<ce:surname>Marder</ce:surname>
<ce:ranking><ce:sup>∗</ce:sup>
</ce:ranking>
</ce:author>
<ce:affiliation><ce:textfn>Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1 Canada</ce:textfn>
</ce:affiliation>
</ce:author-group>
<ce:date-received day="13" month="2" year="1990"></ce:date-received>
<ce:abstract><ce:section-title>Abstract</ce:section-title>
<ce:abstract-sec><ce:simple-para>The crystal and molecular structures of [(η-C<ce:inf>9</ce:inf>
H<ce:inf>7</ce:inf>
)<ce:inf>2</ce:inf>
M] (M = Fe, <ce:bold>1</ce:bold>
; Co, <ce:bold>2</ce:bold>
; Ni, <ce:bold>3</ce:bold>
) and [(η-C<ce:inf>9</ce:inf>
Me<ce:inf>7</ce:inf>
)<ce:inf>2</ce:inf>
Fe], <ce:bold>4</ce:bold>
, are reported, along with a discussion of the correlation between hapticity and the <ce:sup loc="pre">13</ce:sup>
C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both <ce:bold>1</ce:bold>
and <ce:bold>2</ce:bold>
undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of <ce:bold>3</ce:bold>
do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of <ce:bold>4</ce:bold>
were only examined at ambient temperature, where an ordered structure was obtained.</ce:simple-para>
<ce:simple-para>In contrast to the analogous Cp<ce:inf>2</ce:inf>
M series (Cp = η<ce:sup>5</ce:sup>
-C<ce:inf>5</ce:inf>
H<ce:inf>5</ce:inf>
; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η<ce:sup>5</ce:sup>
- toward η<ce:sup>3</ce:sup>
-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni.</ce:simple-para>
<ce:simple-para>The slip values (Δ = avg <ce:italic>d</ce:italic>
(MC(3a),C(7a)) − avg <ce:italic>d</ce:italic>
(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for <ce:bold>1</ce:bold>
–<ce:bold>4</ce:bold>
, respectively. For a “true η<ce:sup>5</ce:sup>
”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η<ce:sup>3</ce:sup>
-”indenyl complexes such as [(η<ce:sup>3</ce:sup>
-C<ce:inf>9</ce:inf>
H<ce:inf>7</ce:inf>
)Ir(PMe<ce:inf>2</ce:inf>
Ph)<ce:inf>3</ce:inf>
]. Therefore, complexes <ce:bold>1</ce:bold>
and <ce:bold>4</ce:bold>
are clearly η<ce:sup>5</ce:sup>
, as predicted on the basis of the 18-electron rule, whereas <ce:bold>2</ce:bold>
and <ce:bold>3</ce:bold>
display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in <ce:bold>3</ce:bold>
are half-way between η<ce:sup>5</ce:sup>
- and η<ce:sup>3</ce:sup>
-coordination modes.</ce:simple-para>
<ce:simple-para>Crystal data for <ce:bold>1</ce:bold>
at 295 K are: monoclinic, <math altimg="si1.gif"><fr shape="sol"><nu><it>P</it>
2<inf>1</inf>
</nu>
<de><it>n</it>
</de>
</fr>
</math>
, <ce:italic>a</ce:italic>
8.030(2), <ce:italic>b</ce:italic>
7.806(2), <ce:italic>c</ce:italic>
10.779(2) Å, β 107.39(1)°, <ce:italic>V</ce:italic>
648.9(2) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 2, structure not refined; at 150 K: monoclinic, <ce:italic>Cc</ce:italic>
, <ce:italic>a</ce:italic>
16.021(4), <ce:italic>b</ce:italic>
15.510(5), <ce:italic>c</ce:italic>
11.187(3) Å, β 115.53(2)°, <ce:italic>V</ce:italic>
2509(1) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 8, <ce:italic>R</ce:italic>
= 0.0306, <ce:italic>R<ce:inf>w</ce:inf>
</ce:italic>
= 0.0332. For <ce:bold>2</ce:bold>
at 295 K: monoclinic, <math altimg="si2.gif"><fr shape="sol"><nu><it>P</it>
2<inf>1</inf>
</nu>
<de><it>n</it>
</de>
</fr>
</math>
, <ce:italic>a</ce:italic>
8.027(2), <ce:italic>b</ce:italic>
7.838(2), <ce:italic>c</ce:italic>
10.936(3) Å, β 107.57(2)°, <ce:italic>V</ce:italic>
655.9(2) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 2, structure not refined; at 150 K: monoclinic, <math altimg="si3.gif"><fr shape="sol"><nu><it>P</it>
2<inf>1</inf>
</nu>
<de><it>c</it>
</de>
</fr>
</math>
, <ce:italic>a</ce:italic>
11.258(3), <ce:italic>b</ce:italic>
7.824(3), <ce:italic>c</ce:italic>
15.256(6) Å, β 108.07(2)°, <ce:italic>V</ce:italic>
1277.7(7) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 4, <ce:italic>R</ce:italic>
= 0.0397, <ce:italic>R<ce:inf>w</ce:inf>
</ce:italic>
= 0.0447. For <ce:bold>3</ce:bold>
, at 150 K: monoclinic, <math altimg="si4.gif"><fr shape="sol"><nu><it>P</it>
2<inf>1</inf>
</nu>
<de><it>n</it>
</de>
</fr>
</math>
, <ce:italic>a</ce:italic>
6.063(1), <ce:italic>b</ce:italic>
20.056(3), <ce:italic>c</ce:italic>
10.703(2) Å, β 94.27(1)°, <ce:italic>V</ce:italic>
1297.9(3) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 4, <ce:italic>R</ce:italic>
= 0.0413, <ce:italic>R<ce:inf>w</ce:inf>
</ce:italic>
= 0.0493. For <ce:bold>4</ce:bold>
, at 295 K: orthorhombic, <ce:italic>Pbcn</ce:italic>
, <ce:italic>a</ce:italic>
14.211(2), <ce:italic>b</ce:italic>
9.284(2), <ce:italic>c</ce:italic>
19.289(4) Å, <ce:italic>V</ce:italic>
2544.8(8) Å<ce:sup>3</ce:sup>
, <ce:italic>Z</ce:italic>
= 4, <ce:italic>R</ce:italic>
= 0.0410, <ce:italic>R<ce:inf>w</ce:inf>
</ce:italic>
= 0.0421.</ce:simple-para>
</ce:abstract-sec>
</ce:abstract>
</head>
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<dateIssued encoding="w3cdtf">1990</dateIssued>
<dateCaptured encoding="w3cdtf">1990-02-13</dateCaptured>
<copyrightDate encoding="w3cdtf">1990</copyrightDate>
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<abstract lang="en">The crystal and molecular structures of [(η-C9H7)2M] (M = Fe, 1; Co, 2; Ni, 3) and [(η-C9Me7)2Fe], 4, are reported, along with a discussion of the correlation between hapticity and the 13C chemical shift of the indenyl ring-junction carbons (C(3a), C(7a)). Single crystals of both 1 and 2 undergo non-destructive and reversible phase changes upon cooling below ca. 240–245 K. The room-temperature structures are disordered; however, the low temperature ones (150 K) are essentially ordered. Crystals of 3 do not display this behavior on cooling to 150 K, and residual anisotropy in certain carbon atoms is ascribed to a minor twinning problem. Crystals of 4 were only examined at ambient temperature, where an ordered structure was obtained. In contrast to the analogous Cp2M series (Cp = η5-C5H5; M = Fe, Co, Ni), which display a gradual symmetric increase in MC distances in the order Fe < Co < Ni, the distortions in the indenyl series are of a fundamentally different nature. Thus, there is a gradual increase in the degree of slip-fold distortion from η5- toward η3-coordination which involves (a) slippage of the metal away from C(3a),C(7a), and (b) folding of the ring system (particularly at C(1),C(3)), in the order Fe < Co < Ni. The slip values (Δ = avg d(MC(3a),C(7a)) − avg d(MC(1),C(3)) are 0.043(4), 0.124(4), 0.418(6), and 0.030(4) Å for 1–4, respectively. For a “true η5”-complex, Δ should be ca. 0 Å, whereas values of ca. 0.69–0.79 Å have been reported for “true η3-”indenyl complexes such as [(η3-C9H7)Ir(PMe2Ph)3]. Therefore, complexes 1 and 4 are clearly η5, as predicted on the basis of the 18-electron rule, whereas 2 and 3 display increasing degrees of distortion in both rings to avoid 19- and 20-electron counts, respectively. The two indenyl rings in 3 are half-way between η5- and η3-coordination modes. Crystal data for 1 at 295 K are: monoclinic, P21 n, a 8.030(2), b 7.806(2), c 10.779(2) Å, β 107.39(1)°, V 648.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, Cc, a 16.021(4), b 15.510(5), c 11.187(3) Å, β 115.53(2)°, V 2509(1) Å3, Z = 8, R = 0.0306, Rw = 0.0332. For 2 at 295 K: monoclinic, P21 n, a 8.027(2), b 7.838(2), c 10.936(3) Å, β 107.57(2)°, V 655.9(2) Å3, Z = 2, structure not refined; at 150 K: monoclinic, P21 c, a 11.258(3), b 7.824(3), c 15.256(6) Å, β 108.07(2)°, V 1277.7(7) Å3, Z = 4, R = 0.0397, Rw = 0.0447. For 3, at 150 K: monoclinic, P21 n, a 6.063(1), b 20.056(3), c 10.703(2) Å, β 94.27(1)°, V 1297.9(3) Å3, Z = 4, R = 0.0413, Rw = 0.0493. For 4, at 295 K: orthorhombic, Pbcn, a 14.211(2), b 9.284(2), c 19.289(4) Å, V 2544.8(8) Å3, Z = 4, R = 0.0410, Rw = 0.0421.</abstract>
<relatedItem type="host"><titleInfo><title>Journal of Organometallic Chemistry</title>
</titleInfo>
<titleInfo type="abbreviated"><title>JOM</title>
</titleInfo>
<genre type="Journal">journal</genre>
<originInfo><dateIssued encoding="w3cdtf">19900811</dateIssued>
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<identifier type="ISSN">0022-328X</identifier>
<identifier type="PII">S0022-328X(00)X1275-2</identifier>
<part><date>19900811</date>
<detail type="volume"><number>394</number>
<caption>vol.</caption>
</detail>
<detail type="issue"><number>1–3</number>
<caption>no.</caption>
</detail>
<extent unit="issue pages"><start>C1</start>
<end>C48</end>
</extent>
<extent unit="issue pages"><start>1</start>
<end>794</end>
</extent>
<extent unit="pages"><start>777</start>
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