Reactions of Ir(CO)(H)(P(p-tolyl)3)3 with SO2 and O2 Mixtures and with H2SO4, Formation of a Sulfate-Bridged Dimer, and Crystal
详细信息 查看全文
- 作者：Cynthia A. Miller ; Thomas S. Janik ; Melvyn Rowen Churchill ; and Jim D. Atwood
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：June 5, 1996
- 年：1996
- 卷：35
- 期：12
- 页码：3683 - 3686
- 全文大小：156K
- 年卷期：v.35,no.12(June 5, 1996)
- ISSN：1520-510X
文摘
Reactions ofHIr(CO)(P(p-tolyl)3)3 withSO2, O2, mixtures of SO2 andO2, and H2SO4 are described.Reactionswith mixtures of SO2/O2 and withH2SO4 lead to a common product,Ir2H4(
-SO4)(P(p-tolyl)3)6,where a bidentateSO42- bridges the iridiumcenters. The complexHIr(CO)(P(p-tolyl)3)3 isstable toward O2 but reacts readily withSO2 to giveHIr(CO)(SO2)(P(p-tolyl)3)2,which was characterized by a crystal structure determination. ThespeciesIr(CO)(H)(SO2)(P(p-tolyl)3)2crystallizes in the centrosymmetric triclinic space groupP
with a = 10.675(1)Å,b = 10.882(1) Å, c = 17.740(2) Å,
= 84.626(10)
, 
= 83.432(10), 
=87.043(10), V = 2036.6(3) Å3,andZ = 2. Diffraction data (Mo K, 2
=4.5-45.0) were collected on a Siemens R3m/V diffractometer, andthestructure was refined to R = 3.00% for 4218 independentreflections with Fo >6
(Fo). Thefive-coordinateiridium(I) center has a distorted environment (closer to trigonalbipyramidal than to square pyramidal) with H(1)-Ir(1)-S(1) = 171.4(23). Bond lengths are Ir-P= 2.303(2) and 2.320(2) Å, Ir-SO2 =2.372(2) Å, Ir-CO =1.906(8) Å, and Ir-H = 1.65(7) Å. TheSO2 ligand has bond distances of S(1)-O(1) =1.442(7) and S(1)-O(2)= 1.441(7) Å, with O(1)-S(1)-O(2) =113.1(4).
-SO4)(P(p-tolyl)3)6,where a bidentateSO42- bridges the iridiumcenters. The complexHIr(CO)(P(p-tolyl)3)3 isstable toward O2 but reacts readily withSO2 to giveHIr(CO)(SO2)(P(p-tolyl)3)2,which was characterized by a crystal structure determination. ThespeciesIr(CO)(H)(SO2)(P(p-tolyl)3)2crystallizes in the centrosymmetric triclinic space groupP with a = 10.675(1)Å,b = 10.882(1) Å, c = 17.740(2) Å, = 84.626(10), = 83.432(10), =87.043(10), V = 2036.6(3) Å3,andZ = 2. Diffraction data (Mo K, 2 =4.5-45.0) were collected on a Siemens R3m/V diffractometer, andthestructure was refined to R = 3.00% for 4218 independentreflections with Fo >6(Fo). Thefive-coordinateiridium(I) center has a distorted environment (closer to trigonalbipyramidal than to square pyramidal) with H(1)-Ir(1)-S(1) = 171.4(23). Bond lengths are Ir-P= 2.303(2) and 2.320(2) Å, Ir-SO2 =2.372(2) Å, Ir-CO =1.906(8) Å, and Ir-H = 1.65(7) Å. TheSO2 ligand has bond distances of S(1)-O(1) =1.442(7) and S(1)-O(2)= 1.441(7) Å, with O(1)-S(1)-O(2) =113.1(4).