Platinum(II) Hydrazido Complexes

Reaction of 1,2-dimethylhydrazine with the platinum hydroxo complex [(dppp)Pt(μ-OH)]2(BF4)2 gives the bridging
1,2-dimethylhydrazido(−2) product [(dppp)2Pt2(μ-η2:η2-MeNNMe)](BF4)2 1. Crystals of 1·CH2Cl2 from CH2Cl2/Et2O are monoclinic (C/2) with a = 19.690(1), b = 18.886(1), c = 17.170 (1) Å, and β = 92.111(1)°. Treatment
of [(dppp)Pt(μ-OH)]2(OTf)2 with 1,1-dimethylhydrazine gives [(dppp)2Pt2(μ−OH)(μ−NHNMe2)](OTf)2 2. Crystals
of 2·CH2Cl2 from CH2Cl2/Et2O are triclinic (P-1) with a = 12.910 (3), b = 13.927(3), c = 17.5872 (3) Å, α =
87.121(3), β = 89.997(4), and γ = 84.728(3)°. Reaction of [(dppp)Pt(μ-OH)]2(OTf)2 with 1 equiv of
phenylhydrazine in CH2Cl2 gives [(dppp)2Pt2(μ-OH)(μ-NHNHPh)](OTf)2 3. Two equivalents of phenylhydrazine
with [(dppp)Pt(μ-OH)]2(X)2 gives [(dppp)Pt(μ-NHNHPh)]2(X)2 4 (X = BF4, OTf). Crystals of 3·ClCH2CH2Cl
from ClCH2CH2Cl/iPr2O are monoclinic (P21/n) with a = 20.990(2), b = 13.098(1), c = 25.773 (2) Å, and β =
112.944(2)°. Crystals of 4(X = BF4)·ClCH2CH2Cl.2(tBuOMe) from ClCH2CH2Cl/tBuOMe are monoclinic (C2/m) with a = 30.508(1), b = 15.203(1), c = 19.049 (1) Å, and β = 118.505(2)°.