[Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)] | 175720-75-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)]
• 英文别名: Pt(CH2C6H4P(o-tolyl)2-C,P)(dimethyldithiocarbamate)；[Pt(2-CH2C6H4P(o-tolyl)2-κC,P)(S2CNMe2)]
• CAS: 175720-75-9
• 化学式: C₂₄H₂₆NPPtS₂
• 分子量: 618.663
• InChiKey: SQKANGGONFPVSF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)] 、 mercury dibromide 以 二氯甲烷 为溶剂， 以87%的产率得到[Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)HgBr(μ-Br)]2
  参考文献：
  名称：

  Reactivity of [M(C∧P)(S₂C-R)] (M = Pd, Pt; C∧P = CH₂-C₆H₄-P(o-tolyl)₂-κC,P; R = NMe₂, OEt) toward HgX₂ (X = Br, I). X-ray Crystal Structures of [Pt{CH₂-C₆H₄P(o-tolyl)₂-κC,P}(S₂CNMe₂)HgI(μ-I)]₂ and [PdBr(S₂COEt){μ-P(o-tolyl)₂-C₆H₄-CH₂-}HgBr]·0.5HgBr₂·C₂H₄Cl₂

  摘要：

  The reaction of the complexes [Pt(C boolean AND P)(S2C-R)] (C boolean AND P = CH2-C6H4-P(o-tolyl)(2)-kappa C,P,R = NMe2, OEt) with an equimolar amount of HgX2 (X = Cl, Br) gives the tetranuclear derivatives [Pt(C boolean AND P)(S2C-R)HgX(mu-X)](2) [R = NMe2, X = Br (3), I (4); R = OEt, X = Br (5), I (6)] containing Pt-->Hg donor-acceptor bonds. The reaction of [Pd(C boolean AND P)(S2CNMe2)] with HgI2 affords the complex [Pd(C boolean AND P)(S2CNMe2)HgI(mu-I)](2) (9) similar to the complexes 3-6; by contrast the reaction of [Pd(C boolean AND P)(S2C-R)] (R = NMe2, OEt2) with HgBr2 leads to the corresponding dinuclear complexes [PdBr(S2C-R)(mu-C boolean AND P)HgBr] [R = NMe2 (10), OEt (11)] with the didentate C boolean AND P cyclometalating ligand, -CH2-C6H4-P(o-tolyl)(2)-C,P (resulting from the C-H activation of the P(o-tolyl)(3)) acting in an unprecedented bridging mode. Compound 4 (C24H26HgI2NPPtS2) crystallizes in the triclinic system, space group P (1) over bar: a = 9.5755(11) Angstrom, b = 11.1754(12) Angstrom, c = 14.501(2) Angstrom, alpha = 84.826(5)degrees, beta = 81.611(7)degrees, gamma = 68.606(9)degrees, V = 1428.5(3) Angstrom(3), and Z = 1. Compound 11.0.5 HgBr2 . C2H4Cl2 (C24H25Br2HgOPPdS2 . 0.5 HgBr2 . C2H4Cl2) crystallizes in the monoclinic system, space group P2(1)/c: a 15.571(2) Angstrom, b = 10.7425(10) Angstrom, c = 19.655(2) Angstrom, beta = 94.741(12)degrees, V = 3276.5(5) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic970584e
• 作为产物：
  描述：

  [Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)HgBr(μ-Br)]2 、 三苯基膦 以 not given 为溶剂， 生成 [Pt(CH2-C6H4-P(o-tolyl)2-κC,P)(dimethyldithiocarbamate)] 、 [(PPh₃)₂Hg₂Br₄]
  参考文献：
  名称：

  Reactivity of [M(C∧P)(S₂C-R)] (M = Pd, Pt; C∧P = CH₂-C₆H₄-P(o-tolyl)₂-κC,P; R = NMe₂, OEt) toward HgX₂ (X = Br, I). X-ray Crystal Structures of [Pt{CH₂-C₆H₄P(o-tolyl)₂-κC,P}(S₂CNMe₂)HgI(μ-I)]₂ and [PdBr(S₂COEt){μ-P(o-tolyl)₂-C₆H₄-CH₂-}HgBr]·0.5HgBr₂·C₂H₄Cl₂

  摘要：

  The reaction of the complexes [Pt(C boolean AND P)(S2C-R)] (C boolean AND P = CH2-C6H4-P(o-tolyl)(2)-kappa C,P,R = NMe2, OEt) with an equimolar amount of HgX2 (X = Cl, Br) gives the tetranuclear derivatives [Pt(C boolean AND P)(S2C-R)HgX(mu-X)](2) [R = NMe2, X = Br (3), I (4); R = OEt, X = Br (5), I (6)] containing Pt-->Hg donor-acceptor bonds. The reaction of [Pd(C boolean AND P)(S2CNMe2)] with HgI2 affords the complex [Pd(C boolean AND P)(S2CNMe2)HgI(mu-I)](2) (9) similar to the complexes 3-6; by contrast the reaction of [Pd(C boolean AND P)(S2C-R)] (R = NMe2, OEt2) with HgBr2 leads to the corresponding dinuclear complexes [PdBr(S2C-R)(mu-C boolean AND P)HgBr] [R = NMe2 (10), OEt (11)] with the didentate C boolean AND P cyclometalating ligand, -CH2-C6H4-P(o-tolyl)(2)-C,P (resulting from the C-H activation of the P(o-tolyl)(3)) acting in an unprecedented bridging mode. Compound 4 (C24H26HgI2NPPtS2) crystallizes in the triclinic system, space group P (1) over bar: a = 9.5755(11) Angstrom, b = 11.1754(12) Angstrom, c = 14.501(2) Angstrom, alpha = 84.826(5)degrees, beta = 81.611(7)degrees, gamma = 68.606(9)degrees, V = 1428.5(3) Angstrom(3), and Z = 1. Compound 11.0.5 HgBr2 . C2H4Cl2 (C24H25Br2HgOPPdS2 . 0.5 HgBr2 . C2H4Cl2) crystallizes in the monoclinic system, space group P2(1)/c: a 15.571(2) Angstrom, b = 10.7425(10) Angstrom, c = 19.655(2) Angstrom, beta = 94.741(12)degrees, V = 3276.5(5) Angstrom(3), and Z = 4.

  DOI：

  10.1021/ic970584e

文献信息

• Reactivity of [M(C∧P)(S₂CNMe₂)] [M = Pt, Pd; C∧P = CH₂−C₆H₄−P(<i>o</i>-tolyl)₂-κ<i>C</i>,<i>P</i>] toward Mercury(II) Carboxylates. X-ray Molecular Structures of [Pt(C∧P)(S₂CNMe₂)(O₂CCF₃)Hg(O₂CCF₃)] and [Pd(S₂CNMe₂){μ-P(<i>o</i>-tolyl)₂−C₆H₄−CH₂−}(μ-O₂CCH₃)Hg(O₂CCH₃)]
  作者：Juan Forniés、Antonio Martín、Violeta Sicilia、Pablo Villarroya

  DOI：10.1021/om990856g

  日期：2000.3.1

  The reaction of the complex [PtCH2−C6H4−P(o-tolyl)2-κC,P}(S2CNMe2)] (A) with an equimolar amount of Hg(O2CR)2 (R = CH3, CF3) gives the binuclear compounds OC-6-23 [Pt(C∧P)(S2CNMe2)(O2CR)Hg(O2CR)] [R = CH3 (1), CF3 (2)] containing a Pt−Hg covalent bond. These compounds result from the cis oxidative addition of the mercury(II) carboxylate to complex A. A concerted mechanism involving a platinum to mercury

  络合物[铂CH的反应2 -C 6 H ^ 4 -P（ø甲苯基）2 -κ Ç，P }（S 2 CNME 2）]（甲）与汞的等摩尔量的（O 2 CR）2（R = CH 3，CF 3），得到的双核化合物OC-6 - 23 [PT（C∧P）（S 2 CNME 2）（O 2 CR）汞柱（O 2 CR）] [R = CH 3（1），CF 3（2）]包含PT-Hg共价键。这些化合物是由羧酸汞（II）的顺式氧化加成到络合物A中产生的。提出了一种涉及铂与汞供体键中间物的协同机制。该复合物的反应[钯CH 2 -C 6 H ^ 4 -P（ø甲苯基）2 -κ Ç，P }（š 2 CNME 2）]（乙）与汞（O 2 CR）2（R =摩尔比为1：1的CH 3，CF 3）生成相应的双核络合物[Pd（S 2 CNMe 2）μ-P（ø甲苯基）2 -C 6 H ^ 4 -CH 2 - }（μ-O 2 CR）汞柱（O 2
• New C,P-Cyclometalated Compounds of Platinum(II) and Platinum(IV) Derived from Tri-<i>o</i>-tolylphosphine
  作者：J. Forniés、A. Martín、R. Navarro、V. Sicilia、P. Villarroya

  DOI：10.1021/om950861u

  日期：1996.4.2

  reaction between [trans-PtCl2(PhCN)2] (PhCN = benzonitrile) and tri-o-tolylphosphine rendered [PtCH2C6H4P(o-tolyl)2-C,P}(μ-Cl)]2 (1), a new C,P-cyclometalated compound of Pt(II). The treatment of 1 with AgClO4 (1:  2) in NCMe gave the mononuclear compound [PtCH2C6H4P(o-tolyl)2-C,P}(NCMe)2]ClO4 (2). Solutions probably containing the cation [PtCH2C6H4P(o-tolyl)2-C,P}(THF)2]+ (THF = tetrahydrofuran) reacted

  [反式-PtCl 2（PhCN）2 ]（PhCN =苄腈）与三邻甲苯基膦反应生成[Pt CH 2 C 6 H 4 P（邻甲苯基）2 - C，P }（μ-Cl ）] 2（1），是一种新的Pt（II）的C，P-环金属化的化合物。在NCMe中用AgClO 4（1：2）处理1得到单核化合物[Pt CH 2 C 6 H 4 P（o- tolyl）2 - C，P}（NCMe）2 ] ClO 4（2）。可能含有阳离子[Pt CH 2 C 6 H 4 P（邻甲苯基）2 - C，P }（THF）2 ] +（THF =四氢呋喃）的溶液与二甲基二硫代氨基甲酸钠（NaS 2 CNMe 2）和乙基钾反应摩尔比为1：1的黄原酸酯（KS 2 COEt）生成单核络合物[Pt CH 2 C 6 H 4 P（o- tolyl）2 - C，P }（S 2 CR）]（R：NMe 2（3），OEt（4））。通过X射线衍射确定3的分子结构。的反应中3和4有Cl
• Nucleophilic behaviour of the neutral complexes [M(C ^ P)(S2CNMe2)] [M = Pd, Pt; C ^ P = CH2C6H4P(C6H4Me-o)2-κ-C,P ] towards Ag(I) and Au(I) compounds. Synthesis (M  = Pd, Pt) and molecular structures (M = Pt) of polynuclear complexes containing M–Ag and M–S bonds
  作者：J. Forniés,、A. Martín、R. Navarro、V. Sicilia、P. Villarroya、A. G. Orpen

  DOI：10.1039/a805099f

  日期：——

  The reactions between [MCH2C6H4P(C6H4Me-o)2}(S2CNMe2)] (M = Pt A, Pd B) and [M′(OClO3)(PPh3)] (M′ = Ag, Au) in 1∶1 ratio yielded [MCH2C6H4P(C6H4Me-o)2}(S2CNMe2)M′(PPh3)]ClO4 (M′ = Ag, M = Pt 1, Pd 2; M′ = Au, M = Pt 3, Pd 4). The molecular structure of 1 indicates that the Ag and Pt atoms are bridged by one S atom of the S2CNMe2 ligand and show a weak interaction between them [Pt–Ag 2.875 (1) Å]. Complexes A and B also react with AgClO4 in 1∶1 molar ratio to give [M2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]ClO4 (M = Pt 5, Pd 6). The X-ray study of 5 revealed that this compound crystallized as a mixture of [Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]ClO4 and [Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag(OH2)}Ag(OClO3)}]ClO4 in 1∶1 molar ratio. In the two different cations only one Ag atom is bonded to Pt, with the Pt–Ag lengths being 2.671 (3) Å for [ Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]+ and 2.752(3) Å for [Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag(OH2)}Ag(OClO3)}]+, both in the range found in other compounds with Pt–Ag bonds. Compounds 5 and 6 react with PPh3 in 1∶2 molar ratio to give compounds 1 and 2 respectively.

  MCH2C6H4P(C6H4Me-o)2}(S2CNMe2)]（M = Pt A, Pd B）和[Mâ²(OClO3)(PPh3)]（Mâ² = Ag、Au）以 1¶1 的比例生成 [MCH2C6H4P(C6H4Me-o)2}(S2CNMe2)Mâ²(PPh3)]ClO4（Mâ²Â = Ag，M = Pt 1，Pd 2；Mâ²Â = Au, M = Pt 3, Pd 4）。1 的分子结构表明，Ag 原子和 Pt 原子由 S2CNMe2 配体的一个 S 原子桥接，它们之间存在微弱的相互作用[PtâAg 2.875 (1) à ]。配合物 A 和 B 还以 1â¶1 摩尔比与 AgClO4 反应，生成 [M2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]ClO4 (M = Pt 5, Pd 6)。对 5 的 X 射线研究表明，该化合物结晶为 [Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]ClO4 和 [Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag(OH2)}Ag(OClO3)}]ClO4 的混合物，摩尔比为 1¶1。在这两种不同的阳离子中，只有一个银原子与铂成键，铂与银的长度分别为：[Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2AgAg(OClO3)}]+为 2.671 (3) Ã，铂与银的长度为 2.752(3) Ã为[Pt2CH2C6H4P(C6H4Me-o)2}2(S2CNMe2)2Ag(OH2)}Ag(OClO3)}]+，两者都在其他具有 PtâAg 键的化合物中发现的范围内。化合物 5 和 6 以 1â¶2 的摩尔比与 PPh3 反应，分别生成化合物 1 和 2。