Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

Eike Bauer; Takanori Shima; Frank A. Hampel; J. A Gladysz

doi:10.1039/b400156g

Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

Eike Bauer, Takanori Shima, Frank A. Hampel, J. A Gladysz

University of Missouri-St. Louis

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

Abstract

<div class="line" id="line-11"> The alkene-containing phosphines PPh((CH2) n CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH2)2)2 (4) are prepared from PPhH2,  n -BuLi, and the corresponding bromoalkenes (1 &ratio; 2 &ratio; 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2–)2)]2 (12) to give the square-planar adducts  trans -(Cl)(C6F5)Pt(PPh((CH2) n CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH2)2)2 (11, 93–73%;  n  = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With 11e, two isomers of  trans -(Cl)(C6F5) <img src="https://www.rsc.org/images/entities/char_e012.gif"/> Pt( <img src="https://www.rsc.org/images/entities/char_e010.gif"/> PPh(CH2)14P <img src="https://www.rsc.org/images/entities/char_e013.gif"/> (C <img src="https://www.rsc.org/images/entities/char_e011.gif"/> H2)14Ph) (15e) are isolated after hydrogenation. Both form  via  dimacrocyclization between the  trans -phosphine ligands, but differ in the dispositions of the PPh rings ( syn , 31%;  anti , 7%). The alternative intraligand metathesis product  trans -(Cl)(C6F5)Pt( <img src="https://www.rsc.org/images/entities/char_e010.gif"/> PPh(C <img src="https://www.rsc.org/images/entities/char_e011.gif"/> H2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H3B·PPh((CH2)6CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH2)2, (ii) cyclization with 2 and hydrogenation to give H3B· <img src="https://www.rsc.org/images/entities/char_e010.gif"/> PPh(C <img src="https://www.rsc.org/images/entities/char_e011.gif"/> H2)14, (iii) deprotection and reaction with 12. The sample derived from 11e contains ≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of  syn -15e,  anti -15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2) n  segment length, 11a undergoes intraligand metathesis to give ( Z , Z )- trans -(Cl)(C6F5)Pt( <img src="https://www.rsc.org/images/entities/char_e010.gif"/> PPh(CH2)2CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH(C <img src="https://www.rsc.org/images/entities/char_e011.gif"/> H2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although 11b does not yield tractable products, 11c gives  syn -( E , E )- trans -(Cl)(C6F5) <img src="https://www.rsc.org/images/entities/char_e012.gif"/> Pt( <img src="https://www.rsc.org/images/entities/char_e010.gif"/> PPh(CH2)4CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH(CH2)4P <img src="https://www.rsc.org/images/entities/char_e013.gif"/> (CH2)4CH <img src="https://www.rsc.org/images/entities/char_e001.gif"/> CH(C <img src="https://www.rsc.org/images/entities/char_e011.gif"/> H2)4Ph) (21%). This structure, and that of the hydrogenation product ( syn -15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give  syn -15d,f (5 and 14% overall).</div><div class="line" id="line-99"> </div>

Original language	American English
Journal	Dalton Transactions
DOIs	https://doi.org/10.1039/b400156g
State	Published - 2004

Disciplines

Physical Sciences and Mathematics
Chemistry

Access to Document

10.1039/b400156gLicense: Unspecified

Cite this

@article{2d7b1919c47c407aa74d774aee84ff0d,

title = "Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands",

abstract = " The alkene-containing phosphines PPh((CH2) n CH CH2)2)2 (4) are prepared from PPhH2,  n -BuLi, and the corresponding bromoalkenes (1 &ratio; 2 &ratio; 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2–)2)]2 (12) to give the square-planar adducts  trans -(Cl)(C6F5)Pt(PPh((CH2) n CH CH2)2)2 (11, 93–73%;  n  = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With 11e, two isomers of  trans -(Cl)(C6F5) Pt( PPh(CH2)14P (C H2)14Ph) (15e) are isolated after hydrogenation. Both form  via  dimacrocyclization between the  trans -phosphine ligands, but differ in the dispositions of the PPh rings ( syn , 31%;  anti , 7%). The alternative intraligand metathesis product  trans -(Cl)(C6F5)Pt( PPh(C H2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H3B·PPh((CH2)6CH CH2)2, (ii) cyclization with 2 and hydrogenation to give H3B· PPh(C H2)14, (iii) deprotection and reaction with 12. The sample derived from 11e contains ≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of  syn -15e,  anti -15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2) n  segment length, 11a undergoes intraligand metathesis to give ( Z , Z )- trans -(Cl)(C6F5)Pt( PPh(CH2)2CH CH(C H2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although 11b does not yield tractable products, 11c gives  syn -( E , E )- trans -(Cl)(C6F5) Pt( PPh(CH2)4CH CH(CH2)4P (CH2)4CH CH(C H2)4Ph) (21%). This structure, and that of the hydrogenation product ( syn -15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give  syn -15d,f (5 and 14% overall). ",

author = "Eike Bauer and Takanori Shima and Hampel, {Frank A.} and Gladysz, {J. A}",

note = "The alkene-containing phosphines PPh((CH2)nCH [[double bond, length as m-dash]] CH2)2)2 (4) are prepared from PPhH2, n-BuLi, and the corresponding bromoalkenes (1 ∶ 2 ∶ 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2-)2)]2 (12) to give the square-planar adducts tr...",

year = "2004",

doi = "10.1039/b400156g",

language = "American English",

journal = "Dalton Transactions",

}

TY - JOUR

T1 - Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

AU - Bauer, Eike

AU - Shima, Takanori

AU - Hampel, Frank A.

AU - Gladysz, J. A

N1 - The alkene-containing phosphines PPh((CH2)nCH [[double bond, length as m-dash]] CH2)2)2 (4) are prepared from PPhH2, n-BuLi, and the corresponding bromoalkenes (1 ∶ 2 ∶ 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2-)2)]2 (12) to give the square-planar adducts tr...

PY - 2004

Y1 - 2004

N2 - The alkene-containing phosphines PPh((CH2) n CH CH2)2)2 (4) are prepared from PPhH2,  n -BuLi, and the corresponding bromoalkenes (1 &ratio; 2 &ratio; 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2–)2)]2 (12) to give the square-planar adducts  trans -(Cl)(C6F5)Pt(PPh((CH2) n CH CH2)2)2 (11, 93–73%;  n  = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With 11e, two isomers of  trans -(Cl)(C6F5) Pt( PPh(CH2)14P (C H2)14Ph) (15e) are isolated after hydrogenation. Both form  via  dimacrocyclization between the  trans -phosphine ligands, but differ in the dispositions of the PPh rings ( syn , 31%;  anti , 7%). The alternative intraligand metathesis product  trans -(Cl)(C6F5)Pt( PPh(C H2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H3B·PPh((CH2)6CH CH2)2, (ii) cyclization with 2 and hydrogenation to give H3B· PPh(C H2)14, (iii) deprotection and reaction with 12. The sample derived from 11e contains ≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of  syn -15e,  anti -15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2) n  segment length, 11a undergoes intraligand metathesis to give ( Z , Z )- trans -(Cl)(C6F5)Pt( PPh(CH2)2CH CH(C H2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although 11b does not yield tractable products, 11c gives  syn -( E , E )- trans -(Cl)(C6F5) Pt( PPh(CH2)4CH CH(CH2)4P (CH2)4CH CH(C H2)4Ph) (21%). This structure, and that of the hydrogenation product ( syn -15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give  syn -15d,f (5 and 14% overall).

AB - The alkene-containing phosphines PPh((CH2) n CH CH2)2)2 (4) are prepared from PPhH2,  n -BuLi, and the corresponding bromoalkenes (1 &ratio; 2 &ratio; 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F5)(S(CH2CH2–)2)]2 (12) to give the square-planar adducts  trans -(Cl)(C6F5)Pt(PPh((CH2) n CH CH2)2)2 (11, 93–73%;  n  = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With 11e, two isomers of  trans -(Cl)(C6F5) Pt( PPh(CH2)14P (C H2)14Ph) (15e) are isolated after hydrogenation. Both form  via  dimacrocyclization between the  trans -phosphine ligands, but differ in the dispositions of the PPh rings ( syn , 31%;  anti , 7%). The alternative intraligand metathesis product  trans -(Cl)(C6F5)Pt( PPh(C H2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H3B·PPh((CH2)6CH CH2)2, (ii) cyclization with 2 and hydrogenation to give H3B· PPh(C H2)14, (iii) deprotection and reaction with 12. The sample derived from 11e contains ≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of  syn -15e,  anti -15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2) n  segment length, 11a undergoes intraligand metathesis to give ( Z , Z )- trans -(Cl)(C6F5)Pt( PPh(CH2)2CH CH(C H2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although 11b does not yield tractable products, 11c gives  syn -( E , E )- trans -(Cl)(C6F5) Pt( PPh(CH2)4CH CH(CH2)4P (CH2)4CH CH(C H2)4Ph) (21%). This structure, and that of the hydrogenation product ( syn -15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give  syn -15d,f (5 and 14% overall).

UR - https://pubs.rsc.org/en/content/articlelanding/2004/dt/b400156g/unauth#!divAbstract

U2 - 10.1039/b400156g

DO - 10.1039/b400156g

M3 - Article

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

Abstract

Disciplines

Access to Document

Other files and links

Cite this