X-ray Crystal Structure and 31P NMR Solution Studies of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3 (dimen = 1,8-Diisocyano-p-menthane). Observation of Partial Site Preference in the Formation of “Outside” Ag and Au Adducts

Andrew G. Sykes; Kent R. Mann

doi:10.1021/ja00176a026

X-ray Crystal Structure and ³¹P NMR Solution Studies of [Ir₂(dimen)₄(PPh₃)Au(PPh₃)](PF₆)₃ (dimen = 1,8-Diisocyano-p-menthane). Observation of Partial Site Preference in the Formation of “Outside” Ag and Au Adducts

Andrew G. Sykes, Kent R. Mann

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

The reaction of [M(PPh₃)₂](PF₆) (M = Ag, Au) with [Ir₂(dimen)₄](PF₆)₂ leads to the formation of heteronuclear complexes of the general formula [Ir₂(dimen)₄(PPh₃)M(PPh₃)](PF₆)₃. Recrystallization of the Au complex from CH₃CN/ether solution afforded crystals of [Ir₂(dimen)₄(PPh₃)Au(PPh₃)](PF₆)₃-CH₃CN (AuIr₂C₈₆H₁₀₅Fi₈N₉P₅) that were the subject of an X-ray crystal structure characterization. The complex crystallizes in the monoclinic space group Cc (No. 9) with Z = 4; a = 24.79 (2), b = 15.792 (6), c = 23.307 (6) Å; ° = 94.15 (4)°; V = 9102 Å³. At convergence, R = 0.055 and R_w = 0.064 for 6382 observed reflections. The crystal contains tripositive cations with a Au(PPh₃)⁺ unit occupying one of the [Ir₂(dimen)₄]²⁺ axial sites and a PPh3 in the second axial position. The PPH₃-Ir₂-Au(PPh₃) moiety features a two-electron two-center Ir-Au bond with a Ir-Au distance of 2.607 (2) Å. Au-P and Ir-P bond distances in the structure are 2.199 (7) and 2.482 (7) Å, respectively. The Ir(CNR)₄ planes are nearly staggered with a twist angle of 39°. The Ir-Ir separation is 2.986 (2) Å.From ³¹P{¹H} NMR solution studies and homonuclear ³¹P{¹H}δ/J-resolved NMR spectroscopy, a nonstatistical distribution of five out of six different geometric isomers is present in CH₂C1₂ solutions of both the Ag⁺ and Au⁺ complexes.

Original language	English (US)
Pages (from-to)	7247-7254
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	112
Issue number	20
DOIs	https://doi.org/10.1021/ja00176a026
State	Published - Jan 1 1990

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X-ray Crystal Structure and ³¹P NMR Solution Studies of [Ir₂(dimen)₄(PPh₃)Au(PPh₃)](PF₆)₃ (dimen = 1,8-Diisocyano-p-menthane). Observation of Partial Site Preference in the Formation of “Outside” Ag and Au Adducts. / Sykes, Andrew G.; Mann, Kent R.
In: Journal of the American Chemical Society, Vol. 112, No. 20, 01.01.1990, p. 7247-7254.

Research output: Contribution to journal › Article › peer-review

@article{64a8151c51134058ae67cee8bea83714,

title = "X-ray Crystal Structure and 31P NMR Solution Studies of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3 (dimen = 1,8-Diisocyano-p-menthane). Observation of Partial Site Preference in the Formation of “Outside” Ag and Au Adducts",

abstract = "The reaction of [M(PPh3)2](PF6) (M = Ag, Au) with [Ir2(dimen)4](PF6)2 leads to the formation of heteronuclear complexes of the general formula [Ir2(dimen)4(PPh3)M(PPh3)](PF6)3. Recrystallization of the Au complex from CH3CN/ether solution afforded crystals of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3-CH3CN (AuIr2C86H105Fi8N9P5) that were the subject of an X-ray crystal structure characterization. The complex crystallizes in the monoclinic space group Cc (No. 9) with Z = 4; a = 24.79 (2), b = 15.792 (6), c = 23.307 (6) {\AA}; ° = 94.15 (4)°; V = 9102 {\AA}3. At convergence, R = 0.055 and Rw = 0.064 for 6382 observed reflections. The crystal contains tripositive cations with a Au(PPh3)+ unit occupying one of the [Ir2(dimen)4]2+ axial sites and a PPh3 in the second axial position. The PPH3-Ir2-Au(PPh3) moiety features a two-electron two-center Ir-Au bond with a Ir-Au distance of 2.607 (2) {\AA}. Au-P and Ir-P bond distances in the structure are 2.199 (7) and 2.482 (7) {\AA}, respectively. The Ir(CNR)4 planes are nearly staggered with a twist angle of 39°. The Ir-Ir separation is 2.986 (2) {\AA}.From 31P{1H} NMR solution studies and homonuclear 31P{1H}δ/J-resolved NMR spectroscopy, a nonstatistical distribution of five out of six different geometric isomers is present in CH2C12 solutions of both the Ag+ and Au+ complexes.",

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T1 - X-ray Crystal Structure and 31P NMR Solution Studies of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3 (dimen = 1,8-Diisocyano-p-menthane). Observation of Partial Site Preference in the Formation of “Outside” Ag and Au Adducts

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N2 - The reaction of [M(PPh3)2](PF6) (M = Ag, Au) with [Ir2(dimen)4](PF6)2 leads to the formation of heteronuclear complexes of the general formula [Ir2(dimen)4(PPh3)M(PPh3)](PF6)3. Recrystallization of the Au complex from CH3CN/ether solution afforded crystals of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3-CH3CN (AuIr2C86H105Fi8N9P5) that were the subject of an X-ray crystal structure characterization. The complex crystallizes in the monoclinic space group Cc (No. 9) with Z = 4; a = 24.79 (2), b = 15.792 (6), c = 23.307 (6) Å; ° = 94.15 (4)°; V = 9102 Å3. At convergence, R = 0.055 and Rw = 0.064 for 6382 observed reflections. The crystal contains tripositive cations with a Au(PPh3)+ unit occupying one of the [Ir2(dimen)4]2+ axial sites and a PPh3 in the second axial position. The PPH3-Ir2-Au(PPh3) moiety features a two-electron two-center Ir-Au bond with a Ir-Au distance of 2.607 (2) Å. Au-P and Ir-P bond distances in the structure are 2.199 (7) and 2.482 (7) Å, respectively. The Ir(CNR)4 planes are nearly staggered with a twist angle of 39°. The Ir-Ir separation is 2.986 (2) Å.From 31P{1H} NMR solution studies and homonuclear 31P{1H}δ/J-resolved NMR spectroscopy, a nonstatistical distribution of five out of six different geometric isomers is present in CH2C12 solutions of both the Ag+ and Au+ complexes.

AB - The reaction of [M(PPh3)2](PF6) (M = Ag, Au) with [Ir2(dimen)4](PF6)2 leads to the formation of heteronuclear complexes of the general formula [Ir2(dimen)4(PPh3)M(PPh3)](PF6)3. Recrystallization of the Au complex from CH3CN/ether solution afforded crystals of [Ir2(dimen)4(PPh3)Au(PPh3)](PF6)3-CH3CN (AuIr2C86H105Fi8N9P5) that were the subject of an X-ray crystal structure characterization. The complex crystallizes in the monoclinic space group Cc (No. 9) with Z = 4; a = 24.79 (2), b = 15.792 (6), c = 23.307 (6) Å; ° = 94.15 (4)°; V = 9102 Å3. At convergence, R = 0.055 and Rw = 0.064 for 6382 observed reflections. The crystal contains tripositive cations with a Au(PPh3)+ unit occupying one of the [Ir2(dimen)4]2+ axial sites and a PPh3 in the second axial position. The PPH3-Ir2-Au(PPh3) moiety features a two-electron two-center Ir-Au bond with a Ir-Au distance of 2.607 (2) Å. Au-P and Ir-P bond distances in the structure are 2.199 (7) and 2.482 (7) Å, respectively. The Ir(CNR)4 planes are nearly staggered with a twist angle of 39°. The Ir-Ir separation is 2.986 (2) Å.From 31P{1H} NMR solution studies and homonuclear 31P{1H}δ/J-resolved NMR spectroscopy, a nonstatistical distribution of five out of six different geometric isomers is present in CH2C12 solutions of both the Ag+ and Au+ complexes.

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