Formation of [Pt(η 3-allyl)(TPPTS) 2] + from reaction of cis-Pt(Cl) 2(TPPTS) 2 with alkenols in water

Derrik S. Helfer; David S. Phaho; Jim D. Atwood

doi:10.1021/om050540a

Formation of [Pt(η ³-allyl)(TPPTS) ₂] ⁺ from reaction of cis-Pt(Cl) ₂(TPPTS) ₂ with alkenols in water

Derrik S. Helfer
, David S. Phaho
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

9 Scopus citations

Abstract

Reactions of alkenols with cis-Pt(Cl) ₂(TPPTS) ₂ (TPPTS = P(m-C ₆H ₄SO ₃Na) ₃) in water result in [Pt(η ³-allyl)(TPPTS) ₂] ⁺ as the exclusive platinum product with 1 equiv of oxidized alkenol. The η ³-allyl is not fluxional in water, and the syn and anti isomers can be distinguished at room temperature. For 3-buten1-ol and 4-penten-1-ol, in addition to the η ³-allyl complex and oxidation of the alkene, catalytic isomerization of the alkene is observed. No reaction occurs for cis-Pt(Cl) ₂(P(p-tolyl) ₃) ₂, cis-Pt(Cl)(THF)-(P(p-tolyl) ₃) ₂ ⁺, or cis-Pt(THF) ₂(P(p-tolyl) ₃) ₂ ²⁺ with the alkenols in THF, indicating the importance of H ₂O. Excess Cl ^- inhibits the reaction. The oxidation product is selectively deuterated. These observations are combined into a proposed mechanism.

Original language	English
Pages (from-to)	410-415
Number of pages	6
Journal	Organometallics
Volume	25
Issue number	2
DOIs	https://doi.org/10.1021/om050540a
State	Published - Jan 16 2006

Access to Document

10.1021/om050540a

Cite this

@article{ee2c641268f24f5ab5b25787f75c8b49,

title = "Formation of [Pt(η 3-allyl)(TPPTS) 2] + from reaction of cis-Pt(Cl) 2(TPPTS) 2 with alkenols in water",

abstract = "Reactions of alkenols with cis-Pt(Cl) 2(TPPTS) 2 (TPPTS = P(m-C 6H 4SO 3Na) 3) in water result in [Pt(η 3-allyl)(TPPTS) 2] + as the exclusive platinum product with 1 equiv of oxidized alkenol. The η 3-allyl is not fluxional in water, and the syn and anti isomers can be distinguished at room temperature. For 3-buten1-ol and 4-penten-1-ol, in addition to the η 3-allyl complex and oxidation of the alkene, catalytic isomerization of the alkene is observed. No reaction occurs for cis-Pt(Cl) 2(P(p-tolyl) 3) 2, cis-Pt(Cl)(THF)-(P(p-tolyl) 3) 2 +, or cis-Pt(THF) 2(P(p-tolyl) 3) 2 2+ with the alkenols in THF, indicating the importance of H 2O. Excess Cl - inhibits the reaction. The oxidation product is selectively deuterated. These observations are combined into a proposed mechanism.",

author = "Helfer, \{Derrik S.\} and Phaho, \{David S.\} and Atwood, \{Jim D.\}",

year = "2006",

month = jan,

day = "16",

doi = "10.1021/om050540a",

language = "English",

volume = "25",

pages = "410--415",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Formation of [Pt(η 3-allyl)(TPPTS) 2] + from reaction of cis-Pt(Cl) 2(TPPTS) 2 with alkenols in water

AU - Helfer, Derrik S.

AU - Phaho, David S.

AU - Atwood, Jim D.

PY - 2006/1/16

Y1 - 2006/1/16

N2 - Reactions of alkenols with cis-Pt(Cl) 2(TPPTS) 2 (TPPTS = P(m-C 6H 4SO 3Na) 3) in water result in [Pt(η 3-allyl)(TPPTS) 2] + as the exclusive platinum product with 1 equiv of oxidized alkenol. The η 3-allyl is not fluxional in water, and the syn and anti isomers can be distinguished at room temperature. For 3-buten1-ol and 4-penten-1-ol, in addition to the η 3-allyl complex and oxidation of the alkene, catalytic isomerization of the alkene is observed. No reaction occurs for cis-Pt(Cl) 2(P(p-tolyl) 3) 2, cis-Pt(Cl)(THF)-(P(p-tolyl) 3) 2 +, or cis-Pt(THF) 2(P(p-tolyl) 3) 2 2+ with the alkenols in THF, indicating the importance of H 2O. Excess Cl - inhibits the reaction. The oxidation product is selectively deuterated. These observations are combined into a proposed mechanism.

AB - Reactions of alkenols with cis-Pt(Cl) 2(TPPTS) 2 (TPPTS = P(m-C 6H 4SO 3Na) 3) in water result in [Pt(η 3-allyl)(TPPTS) 2] + as the exclusive platinum product with 1 equiv of oxidized alkenol. The η 3-allyl is not fluxional in water, and the syn and anti isomers can be distinguished at room temperature. For 3-buten1-ol and 4-penten-1-ol, in addition to the η 3-allyl complex and oxidation of the alkene, catalytic isomerization of the alkene is observed. No reaction occurs for cis-Pt(Cl) 2(P(p-tolyl) 3) 2, cis-Pt(Cl)(THF)-(P(p-tolyl) 3) 2 +, or cis-Pt(THF) 2(P(p-tolyl) 3) 2 2+ with the alkenols in THF, indicating the importance of H 2O. Excess Cl - inhibits the reaction. The oxidation product is selectively deuterated. These observations are combined into a proposed mechanism.

UR - https://www.scopus.com/pages/publications/31544434249

U2 - 10.1021/om050540a

DO - 10.1021/om050540a

M3 - Article

AN - SCOPUS:31544434249

SN - 0276-7333

VL - 25

SP - 410

EP - 415

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Formation of [Pt(η ³-allyl)(TPPTS) ₂] ⁺ from reaction of cis-Pt(Cl) ₂(TPPTS) ₂ with alkenols in water

Abstract

Access to Document

Other files and links

Fingerprint

Cite this