Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide

K. E. Litz; M. M.Banaszak Holl; J. W. Kampf; G. B. Carpenter

Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide

K. E. Litz, M. M.Banaszak Holl, J. W. Kampf, G. B. Carpenter

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

Abstract

The reaction of (Et₃P)₂PtGe[N(SiMe₃)₂]₂ with dioxygen yields (Et₃P)₂Pt(μ-η²-O ₂)Ge[N(SiMe₃)₂]₂ (1). Exposure of 1 to light resulted in a rearrangement to (Et₃P)₂PtO₂Ge[N(SiMe₃) ₂]₂ (2a), the first example of a bidentate, dianionic germanate ligand. The isomerization was judged to occur via an intramolecular O-O bond scission and rotation of the Pt-Ge bond. No free germylene was detected, and the reaction was found to be zero order. An analogue of 2a was prepared by direct reaction of (Ph₃P)₂PtO₂ with Ge[N(SiMe₃)₂]₂ yielding (Ph₃P)₂PtO₂-Ge[N(SiMe₃) ₂]₂ (2b). Addition of SO₂ to 1 results in the formation of the bridging sulfate (Et₃P)₂Pt(μ-η²-SO ₄)-Ge[N(SiMe₃)₂]₂ (3). An infrared spectroscopy study of the sulfate reaction was performed using oxygen-18. The results indicate that direct insertion of SO₂ into the O-O bond does not occur. Formaldehyde was also observed to insert into the Pt-O bond of 1 giving (Et₃P)₂Pt(μ-η²-OCH ₂OO)Ge[N(SiMe₃)₂]₂ (5).

Original language	English
Pages (from-to)	6461-6469
Number of pages	9
Journal	Inorganic Chemistry
Volume	37
Issue number	25
Publication status	Published - 1 Dec 1998
Externally published	Yes

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@article{f82ea8ee8cab4b498b6455daaa07019c,

title = "Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide",

abstract = "The reaction of (Et3P)2PtGe[N(SiMe3)2]2 with dioxygen yields (Et3P)2Pt(μ-η2-O 2)Ge[N(SiMe3)2]2 (1). Exposure of 1 to light resulted in a rearrangement to (Et3P)2PtO2Ge[N(SiMe3) 2]2 (2a), the first example of a bidentate, dianionic germanate ligand. The isomerization was judged to occur via an intramolecular O-O bond scission and rotation of the Pt-Ge bond. No free germylene was detected, and the reaction was found to be zero order. An analogue of 2a was prepared by direct reaction of (Ph3P)2PtO2 with Ge[N(SiMe3)2]2 yielding (Ph3P)2PtO2-Ge[N(SiMe3) 2]2 (2b). Addition of SO2 to 1 results in the formation of the bridging sulfate (Et3P)2Pt(μ-η2-SO 4)-Ge[N(SiMe3)2]2 (3). An infrared spectroscopy study of the sulfate reaction was performed using oxygen-18. The results indicate that direct insertion of SO2 into the O-O bond does not occur. Formaldehyde was also observed to insert into the Pt-O bond of 1 giving (Et3P)2Pt(μ-η2-OCH 2OO)Ge[N(SiMe3)2]2 (5).",

author = "Litz, {K. E.} and Holl, {M. M.Banaszak} and Kampf, {J. W.} and Carpenter, {G. B.}",

year = "1998",

month = dec,

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language = "English",

volume = "37",

pages = "6461--6469",

journal = "Inorganic Chemistry",

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publisher = "American Chemical Society",

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T1 - Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide

AU - Litz, K. E.

AU - Holl, M. M.Banaszak

AU - Kampf, J. W.

AU - Carpenter, G. B.

PY - 1998/12/1

Y1 - 1998/12/1

N2 - The reaction of (Et3P)2PtGe[N(SiMe3)2]2 with dioxygen yields (Et3P)2Pt(μ-η2-O 2)Ge[N(SiMe3)2]2 (1). Exposure of 1 to light resulted in a rearrangement to (Et3P)2PtO2Ge[N(SiMe3) 2]2 (2a), the first example of a bidentate, dianionic germanate ligand. The isomerization was judged to occur via an intramolecular O-O bond scission and rotation of the Pt-Ge bond. No free germylene was detected, and the reaction was found to be zero order. An analogue of 2a was prepared by direct reaction of (Ph3P)2PtO2 with Ge[N(SiMe3)2]2 yielding (Ph3P)2PtO2-Ge[N(SiMe3) 2]2 (2b). Addition of SO2 to 1 results in the formation of the bridging sulfate (Et3P)2Pt(μ-η2-SO 4)-Ge[N(SiMe3)2]2 (3). An infrared spectroscopy study of the sulfate reaction was performed using oxygen-18. The results indicate that direct insertion of SO2 into the O-O bond does not occur. Formaldehyde was also observed to insert into the Pt-O bond of 1 giving (Et3P)2Pt(μ-η2-OCH 2OO)Ge[N(SiMe3)2]2 (5).

AB - The reaction of (Et3P)2PtGe[N(SiMe3)2]2 with dioxygen yields (Et3P)2Pt(μ-η2-O 2)Ge[N(SiMe3)2]2 (1). Exposure of 1 to light resulted in a rearrangement to (Et3P)2PtO2Ge[N(SiMe3) 2]2 (2a), the first example of a bidentate, dianionic germanate ligand. The isomerization was judged to occur via an intramolecular O-O bond scission and rotation of the Pt-Ge bond. No free germylene was detected, and the reaction was found to be zero order. An analogue of 2a was prepared by direct reaction of (Ph3P)2PtO2 with Ge[N(SiMe3)2]2 yielding (Ph3P)2PtO2-Ge[N(SiMe3) 2]2 (2b). Addition of SO2 to 1 results in the formation of the bridging sulfate (Et3P)2Pt(μ-η2-SO 4)-Ge[N(SiMe3)2]2 (3). An infrared spectroscopy study of the sulfate reaction was performed using oxygen-18. The results indicate that direct insertion of SO2 into the O-O bond does not occur. Formaldehyde was also observed to insert into the Pt-O bond of 1 giving (Et3P)2Pt(μ-η2-OCH 2OO)Ge[N(SiMe3)2]2 (5).

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VL - 37

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EP - 6469

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 25

ER -

Active Role of a Germylene Ligand in Promoting Reactions of Platinum Complexes with Oxygen and Sulfur Dioxide

Abstract

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