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Gyroscope-like platinum(IV) complexes of the macrocyclic dibridgehead diphosphine P((CH2)14)3P
Zhu, Yun ; Dey Baksi, Sourajit ; Bhuvanesh, Nattamai , et al. J. Organomet. Chem.,2023,997,122789. DOI: 10.1016/j.jorganchem.2023.122789
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Abstract: Reactions of the platinum(II) dihalide complexes trans-Pt(X)2(P((CH2)14)3P)(X = Cl,trans-4;Br,trans-6) and excess X2 give the platinum(IV) tetrahalide complexes trans-Pt(X)4(P((CH2)14)3P)(trans-5,trans-7) in 84-95% yields. Their crystal structures are determined and the PtXn conformations and bond lengths compared to those of trans-4 and trans-6. In one instance, a reaction of trans-PtBr2(P((CH2)14)3P) (trans-6) and MeMgBr (2.4 equiv) gave not the precedented product cis-Pt(Me)2(P((CH2)14)3P), but rather a small amount of the platinum(IV) tetra-Me complex trans-Pt(Me)4(P((CH2)14)3P) (trans-8), as verified crystallog. and by diagnostic NMR signals. Independent syntheses were attempted. Reactions of trans-PtCl4(P((CH2)14)3P) (trans-5) or trans-PtBr4(P((CH2)14)3P) (trans-7) with excesses of common sources of Me- were unsuccessful. Thus, the free dibridgehead diphosphine P((CH2)14)3P, which can incorporate PtX2 (X = Cl or Br) to give trans-PtCl2(P((CH2)14)3P) (trans-4) or trans-PtBr2(P((CH2)14)3P) (trans-6), was treated with the PtMe4 source Pt2Me8(μ-SMe2)2. However, this gave instead isomeric cis-Pt(Me)4(P((CH2)14)3P) (cis-8), and attempts to establish cis/trans equilibrium were unsuccessful.
Keywords: Platinum(IV) ; Dibridgehead diphosphines ; Methyl complexes ; Crystal structures ; Gyroscopes ; PtX 4 rotators
Purchased from AmBeed: 16921-30-5
CAS No. : | 16921-30-5 | MDL No. : | MFCD00011389 |
Formula : | Cl6K2Pt | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | DPAIVKJGTXERIM-UHFFFAOYSA-H |
M.W : | 485.99 | Pubchem ID : | 61856 |
Synonyms : |
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Signal Word: | Danger | Class: | 6.1,8 |
Precautionary Statements: | P234-P260-P264-P270-P272-P273-P280-P284-P301+P310+P330-P302+P352-P304+P340-P305+P351+P338+P310-P333+P313-P342+P311-P390-P391-P405-P406-P501 | UN#: | 3290 |
Hazard Statements: | H290-H301-H317-H318-H334-H372-H410 | Packing Group: | Ⅱ |
GHS Pictogram: |
A283854[ 16920-93-7 ]
Potassium hexabromoplatinate(iv)
Reason: Different form