Znorg. Chem. 1994,33, 3079-3084
3079
Heterofunctional Ligands Derived from Monooxidized Bis( phosphino)amines. Synthesis and Transition Metal (Rh(I), Pd(II), Pt(I1)) Complexes of the Triphosphorus Ligands ((1minophosphoranyl)amino)phosphine Phosphinic Oxides Ph2PN(R)Ph2P=NP(O) (0Ph)z (R = CH3, C2H5). Crystal and Molecular Structures of the Rhodium(1) and Platinum(I1) Complexes I
I
(PhO)2(0)PN=PPh2N( C2H5)PhzPRh(C0)Cl and (PhO)2(O)PN=PPh2N( C2Hs)Ph2PP/tC12 Maravanji S. Balakrishna, Bernard D. Santarsiero, and Ronald G. CaveU. Department of Chemistry, University of Alberta, Edmonton, AB, Canada T6G 2G2
Received February 9, 1994" Oxidation of bis(dipheny1phosphino)alkylamines with a phosphinic azide gave ambifunctional triphosphorus ligands of the form Ph2PN(R)Ph2P==NP(O)(OPh)2 (R = CH3, C2H5). The 3IP NMR spectra show large values (ca. 100 Hz) for the couplings between the PII1and the adjacent, central, Pv and smaller (ca. 40 Hz) couplings between this central Pv and the terminal Pv. The terminal PIr1did not show observable coupling to the terminal Pv. These ligands complexed readily with Rh(I), Pd(II), or Pt(I1) centers. Crystal structures of the rhodium complex (PhO)z(O)-
P~=PP~~N(C~HS)P~~PR~(CO)C~.CH~CN [at 23 OC, orthorhombic, Pbca (No. 61),a = 20.277(2)A, b = 21.860(2) A, c = 18.498(2) A, V = 8200(1) A3, 2 = 8, R = 0.069,R, = 0.0531 and the platinum complex
(Ph0)2(0)Pk=PPh2N(C2H5)Ph2P&Clr2CH2C12 [at 23 OC, triclinic, Pi (No. 2), a = 11.752(3)A, b = 20.996(4)
/3 = 105.04(2)O,y = 99.04(2)', V = 2236(1) A3,2 = 2,R = 0.049,R, = 0.0431 showed that, in both cases, the ligand was coordinated to the metal through the PII1 and the imine nitrogen to form square planar complexes. The chelate framework structure of the Pt complex was almost planar throughout whereas the Rh complex showed significant puckering of the backbone atoms. For each complex, however, the backbone amine nitrogen is planar and the PI1I-N-Pv angles are close to 120O. The PI1I-N bond lengths lie in the single-bond range in both cases, but this bond is notably shorter in the Pt complex (1.70(1) A) than in the Rh complex (1.777(12) A). In the Pt complex this latter shortening is accompanied by a notable increase in the Pv-amine nitrogen bond (1.67(1)A versus 1.642(12) A in the Rh complex) and the Pv-imine nitrogen bond (1.67(1)A versus 1.580(11) A in the Rh complex), and both of the bonds between the bridging Pv and the substituent nitrogen atoms are of identical length. In contrast the Rh complex shows dissimilar Pv-N bond lengths toward the two different nitrogen atoms. The differences are in part due to the harder character of the Pt(I1) center arising from the presence of two C1 substituents on Pt.
A, c = 9.716(2)A, 01 = 98.75(2)',
Introduction We have previously described',* synthetic, spectroscopic, and structural investigations of coordination compounds of ((iminophosphorany1)amino)phosphines of the general type Ph2PN(R)PR2(E) (R = Ph, Me, etc.; E = S, Se; E = S, Se, NCbH4-p-CH3, NC6Fd-p-CN). All these ligands readily form chelated complexes with metals.'-3 We report here the synthesis of new, related, potentially trifunctional (or multifunctional) triphosphorus ligands of the type Ph2PN(R)Ph2P=NR' (R = Me, Et; R' = NP(0)(0Ph)z) which are readily obtained4 from the parent bis(phosphino)amine and the phosphinic azide (Ph0)2P(O)N,. Coordination compounds of these new ligands with Rh(I), Pd(II), and Pt(I1) centers were prepared, and two examples, one Rh(1) and one Pt(I1) complex, were structurally characterized.
at -78 OC gave the new nitrogen-bridged ((iminophosphorany1)amin0)phosphinephosphinic oxides Ph2PN(R)Ph2PINP(O)(OPh)2 (3,R = CH3; 4, R = C2H4 in good yield (eq 1). Attempts
Results and Discussion The reactions of bis(phosphino)amines, Ph2PN(R)PPh2 (1, R = CHJ; 2, R = C2H5),5with 1 mol of phosphinic azide in CH2Cl2 Abstract published in Advance ACS Abstracts, June 1, 1994. (1) Balakrishna, M. S.; Klein, R.; Uhlenbrock, S.;Pinkerton, A. A.; Cavell, R. G. Inorg. Chem. 1993, 32, 5616. (2) Katti, K. V.; Santarsiero, B. D.; Pinkerton, A. A.; Cavell, R. G. Inorg. Chem. 1993, 32, 5919. (3) Balakrishna, M. S.; Cavell, R. G. Submitted for publication. (4) Balakrishna, M. S.; Klein, R.; Niehaus, M.; Pinkerton, A. A.; Cavell, R. G. Manuscript in preparation. ( 5 ) Ewart, G.;Lane, A. P.; McKechine, J.; Payne, D. S.J . Chem. Soc. 1964, 1543.
Ph
H
to prepare the phenylamino analog through reaction of bis(dipheny1phosphino)phenylamine with limited quantities of this oxo-phosphinic azide under similar reaction conditions led to the
0020-166919411333-3079$04.50/0 0 1994 American Chemical Society
3080 Inorganic Chemistry, Vol. 33, No. 14, 1994
Balakrishna et al.
a
' 4doo ' &so I 24.8 24.4
I
a
,
3 h ' 3i50 # , 24.0
-iioo -iiso' -16.6
-1800' HZ vs H3Po4 ppm vs H3P04
' -ll'.O
b
I
16500 I 101.6
1
I
1
16400 I 101.2
1
1
I
1
1
1woo
I
100.8
I
1
l
I
100.4
I
I
I
I
I
I
I
I
' -6kO '
9000 8950 8900 I I I I 55.8 55.4 55.0 I
4.8
-700 ' -750 -4.2 ' 4 . 6
Hr vs H3P04 ppmvs H3PO4
Figure 1. ,IP{lH) NMR spectra of (a) compound 4 and (b) the Rh complex of the same ligand (9). Table 1. Phosphorus-31 NMR Data for Ligands (3, 4) and Their Complexesa
"pd
(PhO)zP(O)N-PPhzN(CH3)PPh2 (3) (PhO)2P(O)N~PPhzN(CzH5)PPhz(4)
6(P"')
chcm shifts and shift differences, ppm Abb b(PV)[N] A6 6(Pv)[ol
53.9 50.6
100.6 46.7 (P~O)~P(O)N-PP~ZN(CH~)PP~~R~(CO)C~(~) I 50.4 (PhO)~P(O)k-PPh~N(CzH~)PPh~Rh(CO)Cl(9)101.0 (Ph0)2P(O)NmPPhzN(CH3)PPh2PdClz(10) 16.6 22.1 r I (PhO)2P(O)N=PPh2N(C2Hs)PPh2PdC12 (11) 73.2 22.6 r 1 (PhO)2P(O)N=PPh~N(CH3)PPh2ptc12 (12)' 50.7 -3.2 I i (P~O)~P(O)N=PP~~N(C~H~)PP~~P~CIZ (13)' 49.0 -1.6 0
coupling consts, Hz A6
-1 1.o -10.8
26.0 24.3
'Jppm
'JpplOl
99.3 105.0
41.5 45.0
'JPM
53.4
27.4
-4.6
6.4
40.5
30.1
163.6 162.0
55.3
30.4
-4.3
6.5
45.0
29.0
60.3
34.3
-5.4
5.6
33.0
29.0
56.7
31.8
-6.0
4.8
31.6
26.6
61.1
35.1
-6.5
4.5
32.4
25.0
3161.6
59.4
34.5
-6.9
3.9
32.9
30.3
3125.0
All spectra in CDCl3 or CD2C12; 6 ppm vs 85% H3P04; coupling constants in Hz. A6 = G(comp1ex) - G(frcc ligand). Complexes 12 and 13 show
3Jpntpv[ol
coupling (through metal) of 2.5 and 2.2 Hz, respectively.
scheme 1 isolation of major amounts of the acylic phosphazene 5 along onP(OPhX with tetraphenyldiphosphine monoxide 6 and reduced amounts of the desired phosphinophosphinimine 7 as shown in eq 2.4 We attribute this result to hydrolytic cleavage of the P"LN(Ph) bond in 7 by water present in the commercial azide. Although pure 7 could be isolated by crystallization, the difficulty of obtaining reasonable quantities of the material inhibited the investigation of its ligand chemistry. We find, however, that the alkylamino bis(phosphines) 1and 2 are not susceptibleto this type of cleavage a, JP-" and the desired phosphinimino aminophosphines3 and 4 can be R I easily obtained in good yield from the commercial phosphinic 'a y m azide. Complexation chemistry therefore focused on these readily OSP(0Phh obtainable materials. 12 RICH, 13 R G H , The 31P N M R spectra of 3 and 4 show three well separated phosphorus signals with equal relative intensities (see Figure la). The infrared spectra of the complexes show C O absorptions The terminal and Pvpl signals were simple doublets each ] The central P V ~ ~ l at 1988 and 1987 cm-I, respectively, for 8 and 9 which is clearly differently coupled to the central P v [ ~linkage. consistent with the cis related CO/phosphine structure proposed group shows coupling to both kinds of terminal phosphorus and for these complexes. The 3lP NMR spectra are diagnostic, therefore appears as a doublet of doublets in the phosphorus NMR particularly in the case of the Rh(1) complexes which show Rh (Table 1). to PI11 coupling values ( V ~ h p t u )of 163.6 and 162.0 Hz for Reaction of 3 nnd 4 with Rh(I), Pd(II), and Pt(lI) Complexes. complexes 8 and 9, respectively, which clearly indicate that the The new heterodifunctional ligands 3 and 4 each react with [Rhphosphine is coordinated to the metal (Figure 1b). The question (CO)2C1]2 in CH3CN at 25 OC to give five-membered chelates as to which of the remaining base atoms of the ligand completes with the phosphine and the imine nitrogen atoms as donor sites (Scheme 1). The monomeric complexes 8 and 9 are air-stable, the chelate, the imine nitrogen or the phosphoryl oxygen, can crystalline solids. also be addressed by the 31P NMR spectra. Complexes 8 and 9
-
Monooxidized Bis(phosphino)amines
Inorganic Chemistry, Vol. 33, No. 14, 1994 3081
Table 2. Crystal Data for
c(44
L(243)
(P~O)~(O)PN-PP~~N(C~H~)P~ZPR~(CO)C~-CH~CN ( 9 ) and I I (P~O)~(O)PN=PP~~N(C~H~)P~~PP~CI~*~CHZC~~ (13) 13
9
formula
Mr cryst system cryst size, mm space group 0,
A
b, A
c, A
a,deg
8, deg 79 deg
v,A3
F(o00) p(Mo Ka),cm-l h c d , g cm-l
Z
no. of obsd reflcns max 20, deg R" Rwb
C~IH~~CIN~O~ C&3&16NzO5P3Pt P~R~ 868.05 1096.49 orthorhombic triclinic 0.400 X 0.200 X 0.100 0,200 X 0.040 X 0.040 Pbcu (No.61) P1 (No. 2) 20.277(2) 11.752(3) 21.860(2) 20.996(4) 18.498(2) 9.716(2) 98.75(2) 105.04(2) 99.04(2) 8200(1) 2236(1) 3552 1084 6.32 36.74 1.406 1.628 8 2 2130 2681 47.6 45.1 0.069 0.049 0.053 0.043
EIIFd - IFoll/ElFJ. Rw
R
CICH3CN (9) showing the atom-numbering scheme of the complex. Atoms are represented as 20% ellipsoids, and hydrogen atoms have been omitted for clarity.
{Ew(lFd - IFcl)Z/EWIFo12]L/2.
exhibit three distinct phosphorus signals for the PIr1,Pv[N], and PVp]centers upon complexation (Table 1). The chemical shifts of the PI11 centers are also shifted to lower field by approximately 50 ppm relative to the free ligands. The chemical shift of the Pv[N]centers is also shifted by 30 ppm to low field relative to the free ligands, whereas the chemical shifts due to the PVplcenters are shifted by only approximately 6 ppm to lower field strongly suggesting that the Pv[0lcenter is not involved in the coordination to the metal. This conclusion regarding the species in solution is supported by the X-ray structure of 9 (vide infra). Reactions of 3 and 4 with C12Pd(NCPh)2 and Pt(cod)Clz in CH2C12 at 25 OC gave respective chelate complexes 10-13 in good yields. The 3lP(H)NMRspectra of complexes 10-13 exhibit doublets for both the PIr1and PVp]centers and either a doublet ~ ~ ~ ~ or a pseudotriplet (if of doublets (if 2 J p i ~ ~# p2Jpv[N]pv[O]) 2 J p i i p v [ ~= ] 2Jpv[N]pv[O])for the Pv[N] center. Platinum complexes 12 and 13 showed characteristic, very large, lJpiiipt couplings of 3761.6 and 3725 Hz, respectively (therefore PI1[is coordinated to Pt), but no 2Jptpv was observed. The Pt complexes 12 and 13 also show very small 3Jp"MNpV[O] (through metal) couplings of 2.5 and 2.2 Hz, respectively. In contrast similar 3J couplings to the PIIIcenter were not observed for theRh(1) complexes. Relative coordination shifts of the PVplcenter also indicate that the imine nitrogen rather than the phosphoryl oxygen binds to the metal. The structure of complex 13, also established by single-crystal X-ray analysis, is similar to that of the Rh(1) complex, 9, and again shows that the phosphine and imine nitrogen atoms are the chelating atoms. Crystaland Molecular Structuresof Complexes 9 and 13. The structures of complexes 9 and 13 were each determined by singlecrystal X-ray diffraction studies. Crystal data are given in Table 2. Perspective views of the molecules and the numbering schemes are shown in Figures 2 and 3.6 Positional parameters are given in Table 3 and 5 , and selected bond lengths and bond angles are listed in Tables 4 and 6, respectively. The rhodium complex 9, I
I
(P~O)~(O)PN=PP~~N(C~HS)P~~PR~(CO)C~, cocrystallized with 1 mol of CH3CN whereas the platinum complex 13, (PhO)2I
ORTEP"plot of a perspective view of the complex molecule I I in the crystal structure of (P~O)~(O)PN=PP~~N(CZH~)P~~PR~(CO)Figure 2.
I
(O)PN=PPh2N(QHs)Ph2PPtClz, cocrystallized with 2 mol of CH2Cl2. In complex 9 the rhodium metal lies in an approximately square planar environment, with the (Ph0)2P(O)N=PPh2N(CzHs)PPh2 ligand connected in a cis relationship (via the imine ( 6 ) Johnson, C. K.;ORTEE Report ORNL No. 5138; Oak Ridge National Laboratory: Oak Ridge, TN, 1976.
Figure 3. ORTEP" plot of a perspective view of the complex molecule I 1 in the crystal structure of (P~O)~(O)PN=PP~~N(CZH~)P~~PP~C~~ C12 (13) showing the atom-numberingschemeof the complex.Atoms are represented as 20%ellipsoids,and hydrogen atoms have been omitted for clarity.
nitrogen) and the phosphorus(II1) atom to the metal to form a five-membered chelate ring. This central chelate structure is not completely flat. The central square plane defined by the Rh, C (of CO), C1, N(2), and P ( l ) atoms deviated from planarity by up to 0.13(2) to -0.104(4) A . In the backbone, the bridging amine nitrogen N ( 1) is, within the limits defined by the central plane, also essentially coplanar (0.07 A) with the central plane. The backbone phosphorus P(2) however lies well out of the plane (0.484 A) forming the flap of a slightly crinkled envelope. As in previous Rh(1) complex structures of similar heterodifunctional ligands, 9 also shows the carbonyl group to lie in a cis-relationship with the phosphine(II1) center and the carbonyl group lies trans to the more electronegative halogen donor. The platinum atom in complex 13 lies in the center of a welldefined square planar arrangement of the phosphorus(III), the imine nitrogen, and two chlorine atoms about the metal center. The two chlorine atoms are cis as required by the geometry of the bidentate ligand. The entire central framework of the Pt complex including the backbone P(2) and N ( l ) atoms of the chelate ligand lies very close to planarity; all atoms lie within 0.03( 1) A of the plane defined by the central square plane of Pt, C1(1), C1(2), N(2), and P ( l ) atoms. The bridging phosphorus P(2) lies only about 0.09 A out of this plane whereas the amine backbone nitrogen, N(1), lies 0.16 A out of plane again to form the flap of an envelope. All together, however the deviations from central structure planarity are much smaller for the Pt complex than they are for the Rh complex.
Balakrishna et al.
3082 Inorganic Chemistry, Vol. 33, No. 14, 1994 Table 3. Table of Positional Parameters#$ and Thermal Parametersc of the Central Framework Atoms for
Table 5. Positional ParametersE>and Thermal Paramet" of the Central Framework Atoms for
(P~~)~(O)PP(I=-=PP~~N(C~HS)P~~PP~~~-~CH~CI~ (13)d ~~~~
~
atom Cl P(1) P(2) P(3) 0 0(1) O(2) O(3) N(l) N(2) C C(l) C(2) C(11) C(21) C(31) C(41) C(51) C(61)
Y I E,' A2 6.2(3) 0.1781(2) 0.3143(2) 0.1783(2) 5.0(3) 0.1608(2) 0.4447(2) 0.3538(2) 0.0522(2) 0.5032(2) 3.5(2) 0.2857(2) 4.0(3) 0.0703(2) 0.4659(2) 0.1618(2) 10.5(5) 0.2548(7) 0.2789(7) 0.3243(7) 4.6(3) 0.0237(5) 0.5220(5) 0.1475(5) 0.3888(5) 4.6(2) 0.0439(4) 0.1472(5) 0.4691(5) 4.2(2) 0.1358(4) 0.1237(5) 4.1(3) 0.1009(5) 0.5092(6) 0.3471(6) 0.0933(5) 0.4602(5) 3.1(2) 0.2350(6) 0.3082(9) 0.2159(9) 0.3156(11) 8.0(6) 0.0958(9) 0.5709(10) 7.4(5) 0.3922(9) 0.0403(9) 0.5639(10) 9.2(6) 0.4333(10) 4.8(4) 0.2371(8) 0.4924(9) 0.3662(8) 0.1433(8) 0.3992(10) 6.2(5) 0.4286(9) 4.3(4) 0.0309(7) 0.5952(7) 0.2666(8) 3.7(4) -0.0222(7) 0.4552(8) 0.3022(7) 0.0929(9) 0.0120(8) 0.3670(9) 5.1(4) 0.1773(8) 0.5282(9) 4.9(4) 0.1311(8) 0 Estimatedstandarddeviationsin parentheses. b ipsophenylincluded; all other phenyl atoms omitted. Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as (4/3)[a2E(1,1) + b28(2,2) + cZE(3,3) + ob(- y)E(1,2) + a c ( m B)E( 1,3) + b c ( m a)E(2,3)]. Full details for all atoms are given in the supplementary material. X
Table 4. Selected Bond Distances and Bond Angles for I
I
(Ph0)2(O)PN=PPh2N(C2Hs)Ph2PRh(CO)Cl (9) Rh-Cl Rh-P( 1) Rh-N(2) Rh-C P(1)-NU) P(l)-C(11) P(l)-C(21) P(2I-N 1) P(2)-" P(2)-C(31) Cl-Rh-P( 1) C1-Rh-N( 2) Cl-Rh-C P( 1)-Rh-N(2) P( 1)-Rh-C N( 2)-Rh-C Rh-P( 1)-N( 1) Rh-P(l)-C(ll) Rh-P(l)-C(Zl) N(1)-P(l)-C(ll) N(l)-P(l)-C(21) C(ll)-P(l)-C(21) N(l)-P(2)-N(2) N( 1)-P(2)-C(3 1) N(l)-P(2)-C(41) N(2)-P(2)-C(31) N(Z)-P(2)-C(41)
Bond Distances (A) 2.262(4) Pf2)-Cf41) z.oas(sj ~ (j-oi 3 1)' P(3)-0(2) 2.215( 10) P(3)-0(3) 1.813(21) P(3)-N(2) 1.777(12) 1.903(16) 0-C 0(2)-C(51) 1.775(17) 0(3)-C(61) 1.642(12) N(l)-C(l) 1.580(11) C(l)-C(2) 1.807(13) Bond Angles (deg) 172.0(2) C(31)-P(2)4(41) 101.6(3) 0(1)-P(3)-0(2) 80.5(6) O(l)-P(3)-0(3) 83.0(3) O(l)-P(3)-N(2) O(2)-P( 3)-0( 3) 95.1 (6) 176.7(7) 0(2)-P(3)-N(2) 109.2(5 ) O(3)-P( 3)-N(2) 111.0(5) P(3)-0(2)-C(51) 115.9(7) P(3)-0(3)-C(61) 110.1(7) P( 1)-N( 1)-P(2) 103.0(7) P(1)-N(l)-C(l) 107.2(9) P(2)-N(l)-C(l) 99.1(6) Rh-N(2)-P(2) 105.4(7) Rh-N( 2)-P( 3) 117.2(7) P(2)-N(2)-P(3) 118.8(7) Rh-C-0 111.7(6) N(l)-C(l)4(2)
1.884f 15) 1.482iioj 1.568(10) 1.627(10) 1.571(11) 1.17(2) 1.36(2) 1.43(2) 1.47(2) 1.48(2) 105.0(7) 110.2(6) 119.1(6) 117.0(6) 105.5(6) 103.6(6) 99.7(6) 128(1) 122.4(9) 119.4(7) 122(1) 118(1) 120.7(6) 124.4(6) 113.5(7) 173(2) llO(2)
In each of the complexes 9 and 13 the backbone amine nitrogen N ( l ) is planar with PIILN(l)-PV angles 119.4(7) and 120.2( 7 ) O , respectively. The imine nitrogen, N(2), is also planar. The angles N(2)-Rh-P(l) and N(2)-Pt-P( 1) are 83.0(3) and 88.6(3)O, respectively, close to 90°, which suggests that the fivemembered chelate rings are relatively strain free. In complex 13 the Pt-Cl(2) bond distance, 2.293(5) A, which is tram to the imine nitrogen, is notably shorter than the Pt-Cl( 1) bond distance, 2.364(5) A trans to the coordinating phosphine. In general PdC1 or Pt-Cl bond distances decrease as the electronegativity of the trans positioned substituent increases. Similar trends have been observed in our previous work and also by (7)
Appleton, T. G.; Clark, H.C.; Manzer, L.E. Coord. Chem. Reu. 1973, IO, 335.
atom
X
Y
2
0.29035(09) 0.3245(05) 0.2808(05) 0.5663(08) 0.6742(08) -0.0864(09) -0.1173(08) 0.2521(05) 0.2839(05) 0.3 128(05) 0.4336( 11) 0.2095(11) 0.3096(11) 0.2677(12) 0.2947( 12) 0.2678(18) 0.148(02) 0.556(02) -0.019(03) 0.0987( 16) 0.3527( 16) 0.4150(15) 0.1 509(15) 0.5445(19) 0.1917(19)
0.21351(04) 0.2717(02) 0.1185(02) 0.1353(04) 0.1901 (04) 0.2443(04) 0.1423(05) 0.1 5 18(02) 0.2849(02) 0.3726(03) 0.3909(06) 0.3689(05) 0.4171(05) 0.2040(06) 0.2958(06) 0.1796(09) 0.1452(10) 0.1841 (12) 0.1857(15) 0.1029(09) 0.0973(08) 0.3238(08) 0.3084(08) 0.3885(10) 0.4233(10)
0.08206(08) 0.3223(05) 0.1716(05) 0.58 12(08) 0.3861 (09) 0.0334(09) 0.1846(08) -0.1 334(05) -0.1917(04) 0.0648(05) 0.2001 ( 10) 0.1377( 10) -0.0382( 11) -0.2482( 12) -0.0142(12) -0.4007( 18) -0.5076( 18) 0.451(02) 0.105(03) -0.1990( 16) -0.15 19(16) -O.2298(15) -0.2921 (15) 0.1788( 18) 0.2328(20)
E(ca),' A2 2.33(3) 4.1(2) 4.3(2) 12.1 ( 5 ) 12.0(5) 13.4(6) 13.2(5) 2.7(2) 2.6(2) 3.1(2) 3.6(5) 2.8(5) 3.8(5) 2.1(6) 2.1(6) 3.4(9) 6(1) 8.4(7) 10.4(8) 2.7(4) 2.6(4) 2.0(4) 2.1(4) 334) 3.8(5)
a Estimatedstandard deviationsinparentheses. ipsophenyl includcd, all other phenyl atoms omitted. e Anisotropically refined atoms are given in the form of the isotropic equivalent displacement parameter defined as (4/3)[a2E(l,l) + b28(2,2) + &(3,3) + a b ( m y)E(1,2) + a c ( w B)E( 1,3) + bc(cos a)E(2,3)]. Full details for all atoms are given in the supplementary material.
Table 6. Selected Bond Distances and Bond Angles for
r
( P ~ O ) Z ( O ) P N ~ P P ~ Z N ( C ~ H ~(13) )P~~P~CI~ Bond Distances (A) 1.79(2) 2.364(5) P(2)-C(41) 1.61(1) 2.293(5) P(3)-0(1) 1.56(1) 2.18 1( 5 ) P(3)-0(2) 1.47(1) 2.09(1) P(3)-0(3) 1.63(1) 1.70(1) p(3)-~(2) 1.38(2) 1.82(2) P(1)-C(51) 1.44(2) 1.79(2) 0(2)-C(61) 1.49(2) 1.67(1) N(1)-C(1) 1.50(3) 1.67(1) C(l)-C(2) 1.78(2) ~~~
Cl( 1)-Pt-C1(2) Cl( l)-Pt-P(l) Cl( 1)-Pt-N(2) C1(2)-Pt-P( 1) C1(2)-Pt-N(2) P(1)-Pt-N(2) Pt-P( 1)-N( 1) Pt-P( l)-C( 1 1) Pt-P( l)-C(21) N( 1)-P( I)
