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Metal Sulfur-Nitrogen Compounds. Part 19. Novel Complexes of Cu(I) with the S3N-Chelate Ligand. Preparation and Structure of [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] and [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)].

In alkalischem Medium reagiert S7NH mit Cu-Salzen unter Bildung verschiedenartiger Produkte. Mit CuCN entsteht [Cu(S3N)(CN)]−, als [Ph4As][Cu(S3N)(CN)] isoliert. Es kristallisiert monoklin, P21/c, a = 10,499(5), b = 13,418(6), c = 18,032(8) A, β = 91,84°(3), Z = 4.



Aus CuCl2 und S7NH konnen neben den bekannten Komplexionen [Cu(S3N)2]− und [Cu(S3N)Cl]− noch weitere entstehen. Unter bestimmten Bedingungen bleibt der S7N-Ring zum Teil erhalten; es bildet sich [Cu(S3N)(S7N)]−. Das schwerlosliche [(Ph3P)2N][Cu(S3N)(S7N)] kristallisiert monoklin, P21/n, a = 9,335(6), b = 30.984(11), c = 15,108(8) A, β = 102,87°(4), Z = 4.



Bei langen Reaktionszeiten entsteht aus CuCl2 und S7NH [(S3N)Cu(S2O3)Cu(S3N)]− −, bei dem die beiden Cu-Atome durch ein S-Atom eines S2O3− −-Ions verbruckt sind. Das [Ph4As]+-Salz kristallisiert triklin, P1, a = 11,226(6), b = 12,423(6), c = 19,000(10) A, α = 76,47°(4), β 83,98°(4), γ 84,71°(4), Z = 2.



In all diesen Verbindungen ist die Koordination an CuI trigonal-planar und die S3N−-Chelatgruppe in der ublichen Weise uber 2 S-Atome an Cu gebunden.



Metal Sulfur-Nitrogen Compounds. 19. Novel Complexes of CuI with the S3N− Chelate Ligand. Preparation and Structure of [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)], and [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]



In alkaline media S7NH reacts with Cu salts to yield different products. With Cu(CN) the ion [Cu(S3N)(CN)]− is formed, which was isolated as the [Ph4As]+ salt. The crystals are monoclinic, space group P21/c, a = 10.499(5), b = 13.418(6), c = 18.032(8) A, β = 91.84°(3), Z = 4.



Besides the known complex ions [Cu(S3N)2]− and [Cu(S3N)Cl]− still some more may be obtained when CuCl2 is reacted with S7NH: Under special conditions the S7N ring is partly preserved, and [Cu(S3N)(S7N)]− is formed. Its sparingly soluble [(Ph3P)2N]+ salt is monoclinic, space group P21/n, a = 9.335(6), b = 30.984(11), c = 15.108(8) A, β = 102.87°(4), Z = 4.



Using a longer reaction time a dinuclear complex [(S3N)Cu(S2O3)Cu(S3N)]− − results from the reaction of CuCl2 with S7NH. The two Cu atoms are bridged by an S atom of the S2O3− − anion. The [Ph4As]+ salt of the dinuclear complex anion is triclinic, space group P1, a = 11.226(6), b = 12.423(6), c = 19.000(10) A, β = 76.47°(4), β = 83.98°(4), γ = 84.71°(4), Z = 2.



In all these compounds the coordination of CuI is trigonal-planar, the S3N− chelate group coordinates the Cu in the usual way by two S atoms.

Metall‐Schwefelstickstoff‐Verbindungen. 19. Neue Komplexe von CuI mit dem S3N−‐Chelatliganden Darstellung und Struktur von [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] und [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]

Metal Sulfur-Nitrogen Compounds. Part 19. Novel Complexes of Cu(I) with the S3N-Chelate Ligand. Preparation and Structure of [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] and [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)].

References

Metall‐Schwefelstickstoff‐Verbindungen. 19. Neue Komplexe von CuI mit dem S3N−‐Chelatliganden Darstellung und Struktur von [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] und [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]

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