Syntheses and structures of square planar diplatinum butadiynediyl complexes with two different monophosphine ligands on each terminus; probing the feasibility of a new type of inorganic atropisomerism

Article abstract of DOI:10.1016/j.jorganchem.2017.05.006

Reactions of trans-(C₆F₅)(p-tol₃P)₂Pt(Cl) (PtCl) and R₂PhP (1.0 equiv; R = a/Me, b/p-t-BuC₆H₄, c/p-MeOC₆H₄, d/n-Pr; CH₂Cl₂/rt (a) or toluene/reflux (b-d)) give mainly trans-(C₆F₅)(R₂PhP)(p-tol₃P)Pt(Cl) (Pt′Cl-a-d, 89-29%) and some disubstitution products trans-(C₆F₅)(R₂PhP)₂Pt(Cl) (Pt″Cl-a-d, 4–13%). No substitution occurs with t-Bu₂PhP. However, (cod)(C₆F₅)Pt(Cl) and t-Bu₂PhP (2.7 equiv; toluene/reflux) react to give trans-(C₆F₅)(t-Bu₂PhP)₂Pt(Cl) (Pt″Cl-e, 64%), which upon treatment with p-tol₃P (1.0 equiv, toluene/reflux) yields trans-(C₆F₅)(t-Bu₂PhP)(p-tol₃P)Pt(Cl) (Pt′Cl-e, 91%). Additions of excess butadiyne to Pt′Cl-a-d (CH₂Cl₂, cat. CuI, HNEt₂) afford the butadiynyl complexes trans-(C₆F₅)(R₂PhP)(p-tol₃P)Pt(C≡C)₂H (Pt′C₄H-a-d, 36–77%), but Pt′Cl-e does not similarly react. Cross couplings of Pt′Cl-a-c and Pt′C₄H-a-c (cat. CuI, HNEt₂) give mixtures of diplatinum butadiynyl complexes in which the two unlike phosphine ligands scramble over all four positions (PtC₄Pt, PtC₄Pt′-a-c, PtC₄Pt″-a-c, Pt′C₄Pt′-a-c, Pt′C₄Pt″-a-c, Pt″C₄Pt″-b; TLC separable, 27-2% each). A modified coupling recipe is tested with Pt′Cl-b,d and Pt′C₄H-b,d (t-BuOK, KPF₆, cat. CuCl), and gives Pt′C₄Pt′-b,d (21–76%) with only traces of scrambling. Crystal structures of Pt″Cl-e, Pt′C₄H-a, Pt′C₄Pt′-a-d, and PtC₄Pt″-b are determined, and the endgroup/endgroup interactions analyzed. Low temperature NMR spectra do not reveal any dynamic processes.

Full text of DOI:10.1016/j.jorganchem.2017.05.006

Accepted Manuscript
Syntheses and structures of square planar diplatinum butadiynediyl complexes with
two different monophosphine ligands on each terminus; probing the feasibility of a
new type of inorganic atropisomerism
Sandip Dey, Tianyi Zhang, Nattamai Bhuvanesh, John A. Gladysz
PII:
S0022-328X(17)30292-9
10.1016/j.jorganchem.2017.05.006
JOM 19932
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 7 January 2017
Revised Date: 24 April 2017
Accepted Date: 4 May 2017
Please cite this article as: S. Dey, T. Zhang, N. Bhuvanesh, J.A. Gladysz, Syntheses and structures of
square planar diplatinum butadiynediyl complexes with two different monophosphine ligands on each
terminus; probing the feasibility of a new type of inorganic atropisomerism, Journal of Organometallic
Chemistry (2017), doi: 10.1016/j.jorganchem.2017.05.006.
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ACCEPTED MANUSCRIPT
!
!** REVISED **!!
Syntheses and Structures of Square Planar Diplatinum Butadiynediyl Complexes
with two Different Monophosphine Ligands on each Terminus;
Probing the Feasibility of a New Type of Inorganic Atropisomerism
Sandip Dey, Tianyi Zhang, Nattamai Bhuvanesh, and John A. Gladysz*
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas
§
77842-3012, USA
ABSTRACT
Reactions of trans-(C F )(p-tol P) Pt(Cl) (PtCl) and R PhP (1.0 equiv; R = a/Me, b/p-t-BuC -
6
5
3
2
2
6
H , c/p-MeOC H , d/n-Pr; CH Cl /rt (a) or toluene/reflux (b-d)) give mainly trans-(C F )(R -
4
6 4
2
2
6 5
2
PhP)(p-tol P)Pt(Cl) (Pt'Cl-a-d, 89-29%) and some disubstitution products trans-(C F )(R Ph-
3
6 5
2
P) Pt(Cl) (Pt"Cl-a-d, 4-13%). No substitution occurs with t-Bu PhP. However, (cod)(C F )Pt-
2
2
6 5
(
Cl) and t-Bu PhP (2.7 equiv; toluene/reflux) react to give trans-(C F )(t-Bu PhP) Pt(Cl) (Pt"-
2 6 5 2 2
Cl-e, 64%), which upon treatment with p-tol P (1.0 equiv, toluene/reflux) yields trans-(C F )(t-
3
6 5
Bu PhP)(p-tol P)Pt(Cl) (Pt'Cl-e, 91%). Additions of excess butadiyne to Pt'Cl-a-d (CH Cl , cat.
2
3
2
2
CuI, HNEt ) afford the butadiynyl complexes trans-(C F )(R PhP)(p-tol P)Pt(C≡C) H (Pt'C -
2
6 5
2
3
2
4
H-a-d, 36-77%), but Pt'Cl-e does not similarly react. Cross couplings of Pt'Cl-a-c and Pt'C H-
4
a-c (cat. CuI, HNEt ) give mixtures of diplatinum butadiynyl complexes in which the two unlike
2
phosphine ligands scramble over all four positions (PtC Pt, PtC Pt'-a-c, PtC Pt"-a-c, Pt'C -
4
4
4
4
Pt'-a-c, Pt'C Pt"-a-c, Pt"C Pt"-b; TLC separable, 27-2% each). A modified coupling recipe is
4
4
tested with Pt'Cl-b,d and Pt'C H-b,d (t-BuOK, KPF , cat. CuCl), and gives Pt'C Pt'-b,d (21-
4
6
4
7
6%) with only traces of scrambling. The crystal structures of Pt"Cl-e, Pt'C H-a, Pt'C Pt'-a-d,
4 4
and PtC Pt"-b are determined, and the endgroup/endgroup interactions analyzed. Low tempera-
4
ture NMR spectra do not reveal any dynamic processes.
key words: platinum, phosphine ligands, sp carbon chains, substitution, Hagihara coupling, low
temperature NMR, crystallography
Highlights
The complexes (C F )(R PhP)(p-tol P)Pt(X) (X = Cl/(C≡C) H) are prepared with diverse R
6
5
2
3
2
Hagihara couplings give (C F )(L)(L')Pt(C≡C) Pt(L)(L')(C F ) with L/L' scrambling
6
5
2
6 5
NMR spectra/structures of diplatinum complexes are analyzed regarding atropisomerism
§
Current address: Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
*
Corresponding author. Fax: 979 845 5629. E-mail address: gladysz@mail.chem.tamu.edu
submitted to J. Organomet. Chem. for the special issue dedicated to Prof. Richard Adams
dedication: "to our friend Rick Adams, a source of inspiration and counsel for over forty years"
-
1-

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■
INTRODUCTION
There is an extensive literature of complexes in which two square planar platinum(II)
fragments cap butadiynediyl or -C≡C-C≡C- moieties.1-3 There is also an extensive literature in-
volving higher homologs with as many as 28 sp carbon atoms.1c,2-6 However, there are a number
of interesting properties or phenomena that are uniquely associated with shorter sp carbon
bridges. For example, the platinum(II)/platinum(III) radical cations generated by one electron
oxidations are much more stable at modest chain lengths.2a,b,g,7
8
9
In a recent paper, we described a quest for atropisomers derived from diplatinum eth-
ynediyl or PtC≡CPt complexes.10 The idea was that with appropriate substitution patterns, as ex-
emplified in Scheme 1 with adducts that bear two different trans disposed monophosphine lig-
ands on each platinum, it might be possible to separate enantiomers or diastereomers with an axis
of chirality. Alternatively, slow interconversion could be established by NMR techniques. To
date, these efforts have not resulted in a demonstration of atropisomerism. However, this is likely
because the phosphine ligands initially employed were not bulky enough (e.g., X/Y = Ph/Me in
I). Promising second generation targets are easily envisioned (e.g., X/Y = Ph/t-Bu or i-Pr/o-
C H X).
6
4
Scheme 1. Enantiomeric atropisomers derived from diplatinum ethynediyl complexes. The Y groups are
diastereotopic and potentially distinguishable by NMR.
In laying the groundwork for these studies, related complexes with longer PtC≡CC≡CPt
bridges were also investigated. Although in retrospect there was little chance of detecting atrop-
isomerism in such species, they provided valuable testing grounds for syntheses of coupling part-
ners, such as platinum chloride complexes with the types of monophosphine ligands in Scheme 1,
-2-

ACCEPTED MANUSCRIPT
11
trans-(Ar)(R PhP)(p-tol P)Pt(Cl). They also revealed problematic phosphine scrambling pro-
2
3
cesses under certain coupling conditions, and "standard" protocols that became unreliable in the
presence of bulkier phosphine ligands. Furthermore, several crystal structures that help visualize
the magnitudes of the endgroup/endgroup interactions, which must underpin any atropisomerism,
could be determined. Accordingly, in this full paper, a detailed account of this previously undis-
closed work is presented.
■
RESULTS
. Syntheses of monoplatinum complexes trans-(C F )(R PhP)(p-tol P)Pt(Cl). The
1
6
5
2
3
2
a
previously reported platinum chloride complex trans-(C F )(p-tol P) Pt(Cl) (PtCl) and Me2-
6
5
3
2
PhP (1.0 equiv) were combined in CH Cl at room temperature. As shown in Scheme 2 (top),
2
2
workup gave the monosubstitution product trans-(C F )(Me PhP)(p-tol P)Pt(Cl) (Pt'Cl-a) as a
6
5
2
3
white solid in 89% yield. In some cases, small amounts of PtCl remained, or the disubstituted
byproduct trans-(C F )(Me PhP) Pt(Cl) (Pt"Cl-a) was detected (each <4%). In these cases, Pt'-
6
5
2
2
Cl-a was purified chromatographically. The identity of Pt"Cl-a was confirmed by an independ-
ent synthesis from [(C F )(tht)Pt( -Cl)] and Me PhP (73%; Scheme 2, bottom). This route has
µ
6
5
2
2
been used to prepare many related platinum bis(phosphine) complexes.2a,c,5h,j
Similar reactions were carried out with three other phosphines of the formula R PhP (R =
2
alkyl or aryl; b-d in Scheme 2). With the triarylphosphines (p-t-BuC H ) PhP and (p-MeOC -
6
4 2
6
H ) PhP, no reactions with PtCl occurred over the course of 16 h in refluxing CH Cl . Howev-
4
2
2
2
er, after 22 h in refluxing toluene, the target complexes trans-(C F )(p-tol P)((p-t-BuC H ) Ph-
6
5
3
6 4 2
P)Pt(Cl) (Pt'Cl-b) and trans-(C F )(p-tol P)((p-MeOC H ) PhP)Pt(Cl) (Pt'Cl-c) could be isol-
6
5
3
6 4 2
ated in 29-42% yields following chromatography.
When PtCl and n-Pr PhP were combined in CH Cl or toluene at room temperature,
2
2
2
conversion to trans-(C F )(p-tol P)(n-Pr PhP)Pt(Cl) (Pt'Cl-d) was slow and incomplete. How-
6
5
3
2
ever, the yield of Pt'Cl-d improved to 42% when the sample was refluxed in toluene (6 h). In
each of these reactions, smaller amounts of the disubstituted byproducts Pt"Cl-b-d were also ob-
tained, as verified by independent syntheses (Scheme 2, bottom). Thus, not all of the starting Pt-
-3-

ACCEPTED MANUSCRIPT
Cl was consumed.
F
F
F
Pp-tol3
Pt Cl
F
Pp-tol3
F
PtCl
1
.0 equiv R = a, Me; CH Cl , rt, 16 h
2 2
R PhP
2
b, p-C H t-Bu; toluene, reflux, 22 h
6 4
c, p-C H OMe; toluene, reflux, 22 h
6
4
d, n-Pr; toluene; rt, 16 h, reflux, 6 h
F
F
F
F
F
F
F
F
F
F
F
Pp-tol3
Pt Cl
Pp-tol3
Pt Cl
PPhR2
Pt Cl
+
+
F
Pp-tol3
PPhR2
PPhR2
F
F
F
PtCl
Pt'Cl
a, PtCl/Pt'Cl-a/Pt''Cl-a
4% / 89% / 04%
b, PtCl/Pt'Cl-b/Pt''Cl-b
4% / 29% / 10%
c, PtCl/Pt'Cl-c/Pt''Cl-c
8% / 42% / 13%
d, PtCl/Pt'Cl-d/Pt''Cl-d
7% / 42% / 10%
Pt''Cl
0
2
2
2
F
F
2.0-2.2 equiv
F
R PhP/Pt
2
F
F
F
F
S
Cl
PPhR
Pt Cl
2
CH Cl , 18 h
2
2
F
Pt
F
Pt
F
F
Cl
S
PPhR2
F
F
R = a, Me; 73%, (Pt''Cl-a)
F
F
b, p-C H t-Bu; 76%, (Pt''Cl-b)
6
4
c, p-C H OMe; 52%, (Pt''Cl-c)
6
4
d, n-Pr; toluene; 60%, (Pt''Cl-d)
Scheme 2. Syntheses of monoplatinum complexes trans-(C F )(R PhP)(p-tol P)Pt(Cl) (Pt'Cl; top) and trans-
6
5
2
3
(
C F )(R PhP) Pt(Cl) (Pt"Cl; bottom).
6 5 2 2
Analogous complexes with the bulkier phosphine t-Bu PhP were sought, but no reaction
2
took place with PtCl in refluxing toluene. Thus, alternative routes were explored as summarized
in Scheme 3. First, reactions of [(C F )(tht)Pt(µ-Cl)] and excess t-Bu PhP in CH Cl or reflux-
2 2 2 2
6
5
ing toluene yielded the monophosphine complex (C F )(t-Bu PhP)(tht)Pt(Cl) (1) instead of the
6
5
2
-4-

ACCEPTED MANUSCRIPT
target bis(phosphine) complex trans-(C F )(t-Bu PhP) Pt(Cl) (Pt"Cl-e; compare to Scheme 2,
6
5
2
2
bottom). The stereochemistry depicted in Figure 1 was confirmed by a crystal structure (below).
Subsequent reactions of 1 with the phosphines Et P or p-tol P in refluxing toluene resulted in t-
3
3
Bu PhP displacement. The two-fold substitution products trans-(C F )(Et P) Pt(Cl) or trans-
2
6 5
3
2
2
a,c
(
C F )(p-tol P) Pt(Cl) (PtCl) described earlier
were isolated.
6
5
3
2
F
F
not detected:
F
2
.4 equiv
S
F
F
F
S
Cl
F
F
F
F
t-Bu PhP/Pt
PPht-Bu2
2
F
Pt
F
Pt
F
Pt
PPht-Bu2
F
F
Pt Cl
Cl
S
2
CH Cl2
F
F
F
PPht-Bu2
or
Cl
toluene,
reflux, 15 h
F
1, 77%
F
R' P (R' = Et, p-tol)
toluene, reflux, 15 h
3
B
not detected (route B):
2
.2-2.3 equiv/Pt
F
F
F
A
PR'3
Pt Cl
PR'3
R' P (R' = Et, p-tol)
3
F
F
F
F
PR'3
F
F
Pt Cl
F
PPht-Bu2
t-Bu PhP, CH Cl or
2
2
2
toluene, reflux, 16 h
×
F
F
2.7 equiv
t-Bu PhP
toluene
reflux
1.0 equiv
p-tol3P
toluene
reflux
F
2
F
F
F
F
F
F
F
F
F
Pp-tol3
PPht-Bu2
Pt
F
F
Pt Cl
F
Pt Cl
Cl
PPht-Bu2
PPht-Bu2
Pt''Cl-e, 64%
Pt'Cl-e, 91%
C F Li,
6
5
THF
×
t-Bu PhP,
H O/ethanol
2
2
PPht-Bu2
Pt Cl
Cl
2, 89%
K PtCl
2
4
PPht-Bu2
Scheme 3. Successful and unsuccessful routes to the monoplatinum complexes trans-(C F )(t-Bu PhP)(p-
6
5
2
tol P)Pt(Cl) (Pt"Cl-e) and trans-(C F )(t-Bu PhP)(p-tol P)Pt(Cl) (Pt'Cl-e).
3
6 5
2
3
-5-

ACCEPTED MANUSCRIPT
Next, the previously reported dichloride complex trans-(t-Bu PhP) Pt(Cl) (2) was syn-
2
2
2
thesized by a slight modification of the literature procedure (Scheme 3, bottom).12 The 1JPPt
value (2542 Hz) indicated a trans stereochemistry,13 in accord with a crystal structure. Howev-
14
1
5
er, subsequent additions of C F Li (prepared in situ from n-BuLi and C F Br) in either 1:1 or
6
5
6 5
1
:2 stoichiometries gave mainly starting material. Up to 20% conversion to a new species could
be observed in some experiments, but the properties were not appropriate for the target molecule.
Finally, routes involving the previously described cyclooctadiene complex (cod)(C F )-
6
5
Pt(Cl) were investigated (Scheme 3, bottom).16 No reaction took place with t-Bu PhP (2.7
2
equiv) at room temperature, but trans-(C F )(t-Bu PhP) Pt(Cl) (Pt"Cl-e) formed cleanly in re-
6
5
2
2
fluxing toluene. A 64% yield was isolated after workup. A subsequent reaction with p-tol P (1.0
3
equiv) in refluxing toluene gave the target complex Pt'Cl-e in 91% yield.
2
. Syntheses of butadiynyl complexes trans-(C F )(R PhP)(p-tol P)Pt(C≡C) H (Pt'-
6 5 2 3 2
C H). The next objective was to convert the chloride complexes Pt'Cl-a-e to the corresponding
4
butadiynyl complexes. As shown in Scheme 4 (top), conditions that were effective in an earlier
2
a
synthesis of trans-(C F )(p-tol P) Pt(C≡C) H (PtC H) were applied to Pt'Cl-a (excess buta-
6
5
3
2
2
4
diyne, HNEt , cat. CuI). A chromatographic workup gave the target complex trans-(C F )(Me -
2
6 5
2
PhP)(p-tol P)Pt(C≡C) H (Pt'C H-a) in 36% yield, together with lesser amounts of the phos-
3
2
4
phine scrambling products PtC H (16%) and Pt"C H-a (10%). In an alternative approach, the
4
4
butadiynyl complex PtC H was treated with Me PhP (1.0 equiv, CH Cl , 18 h). Chromatogra-
4
2
2
2
phy gave a comparable product distribution: Pt'C H-a, 30%, PtC H, 18%, Pt"C H-a, 11%.
4
4
4
When the di(n-propyl)phenylphosphine chloride complex Pt'Cl-d and butadiyne were si-
milarly reacted, NMR analyses showed the formation of a 92:4:4 mixture of the target complex
Pt'C H-d and the phosphine scrambling products PtC H and Pt"C H-d. Crystallization afford-
4
4
4
ed pure Pt'C H-d in 73% yield. Interestingly, the two complexes with triarylphosphine ligands,
4
Pt'Cl-b,c, did not give detectable phosphine scrambling. Workups afforded the butadiynyl com-
plexes Pt'C H-b,c in 75-77% yields. As summarized in Scheme 4 (bottom), all attempts to re-
4
place the chloride ligand in Pt'Cl-e by alkynyl ligands were unsuccessful. Alternative cross
-6-

ACCEPTED MANUSCRIPT
coupling protocols (see also below)2d involving t-BuOK base and KPF gave no reaction.
6
F
F
Pp-tol3 R = a, Me
b, p-C H t-Bu
6
4
F
Pt Cl
c, p-C H OMe
6
4
PPhR2
d, n-Pr
F
F
Pt'Cl
HNEt , cat. CuI,
2
H(C≡C) H
2
F
F
F
F
F
F
F
F
F
F
Pp-tol3
Pp-tol3
PPhR2
F
Pt C C C C H
Pp-tol3
+
F
Pt C C C C H
PPhR2
+
F
Pt C C C C H
PPhR2
F
F
PtC H
Pt'C H-a-d
Pt''C H-a-d
4
4
4
a, 16% / 36% / 10%
b, <2% / 77% / <2%
c, <2% / 75% / <2%
d, 04% / 92% / 04% (in situ)
<
2% / 73% / <2% (after crystallization)
F
F
F
F
Pp-tol3
HNEt , cat. CuI,
2
H(C≡C) H or
2
F
Pt C C C C H
HC≡CSiR (R = Me, Et)
3
F
F
F
F
PPht-Bu2
Pp-tol3
Pt Cl
or
Pt'C H-e
4
F
PPht-Bu2
t-BuOK, KPF , cat. CuI
F
F
6
Pp-tol3
H(C≡C) H, THF/ meth
2
anol
Pt'Cl-e
F
Pt C C SiR
PPht-Bu2
3
F
F
Scheme 4. Successful and unsuccessful syntheses of monoplatinum butadiynyl and alkynyl complexes.
3
. Syntheses of diplatinum butadiynediyl complexes. Numerous diplatinum butadiyne-
diyl complexes have been prepared by Hagihara heterocouplings of platinum butadiynyl and pla-
tinum chloride complexes.2a,c,d Thus, as shown in Scheme 5, equimolar quantities of the butadi-
ynyl complexes Pt'C H-a-c (see Scheme 4) and chloride complexes Pt'Cl-a-c (see Scheme 2)
4
were combined in HNEt in the presence of a catalytic amount of CuCl. After 66-88 h at 45-50
2
°
C, workups gave mixtures of five to six diplatinum butadiynediyl complexes. Although the indi-
vidual yields were low, they could be separated by silica gel column chromatography.
It quickly became apparent that the many products were derived from scrambling of the
phosphine ligands. In our previous applications of Hagihara coupling reactions, all of the phos-
-7-

ACCEPTED MANUSCRIPT
phine ligands had been identical, so this phenomenon remained undetected. In accord with nom-
enclature introduced above, the three possible endgroups could be designated Pt ((C F )(p-tol -
6
5
3
P) Pt), Pt' ((C F )(p-tol P)(R PhP)Pt), and Pt" ((C F )(R PhP) Pt). These can in turn code for
2
6 5
3
2
6 5
2
2
the six possible products, PtC Pt, PtC Pt', PtC Pt", Pt'C Pt', Pt'C Pt" and Pt"C Pt".
4
4
4
4
4
4
Scheme 5. Syntheses of diplatinum butadiynyl complexes.
In the case where the phenylphosphine substituents (R ) were Me (a), five diplatinum
2
complexes were isolated: PtC Pt, 3%; PtC Pt'-a, 23%; PtC Pt"-a, 12%; Pt'C Pt'-a, 27%; Pt'-
4
4
4
4
C Pt"-a, 4%. The R values decreased as the number of Me PhP ligands increased. All were air
4
f
2
-8-

ACCEPTED MANUSCRIPT
1
13
1
31
1
stable yellow solids, and were characterized by NMR ( H, C{ H}, P{ H}) and microanalys-
es, as summarized in the experimental section. The structures readily followed from the NMR
properties, principal details of which are described below.
In the case where the phenylphosphine substituents were p-t-BuC H (b), six diplatinum
6
4
complexes were isolated: PtC Pt, 2%; PtC Pt'-b, 8%; PtC Pt"-b, 9%; Pt'C Pt'-b, 3%; Pt'C -
4
4
4
4
4
Pt"-b, 8%; Pt"C Pt"-b, 2%. In the case where the phenylphosphine substituents were p-MeO-
4
C H (c), five complexes were isolated as summarized in Scheme 5. This coupling was some-
6
4
what slower, so a significant amount of unreacted chloride complex Pt'Cl-c (26%) was recover-
ed, together with traces of the scrambled analog PtCl (1%).
Given these disappointing results, attention was turned to an alternative recipe for cross
coupling metal chloride and terminal alkynyl complexes. It had been shown that when THF/me-
thanol solvent mixtures were employed with slight excesses of t-BuOK and KPF and a catalytic
6
amount of CuCl, diplatinum butadiynediyl complexes could be isolated in good yields.2d This
protocol was optimized using equimolar quantities of the p-tol P substituted reaction partners
3
1
7
trans-(C F )(p-tol P) Pt(C≡C) H (PtC H) and PtCl. As described elsewhere, workup gave
6
5
3
2
2
4
the known complex PtC Pt in 73% yield.
4
F
F
F
F
F
Pp-tol3
Pt
PPhR2
p-tol
Cl Pt
R PhP
3
P
F
C
C
C
CH
+
F
2
F
F
F
Pt'C H-b,d
Pt'Cl-b,d
4
t-BuOK, KPF6
cat. CuCl
THF/methanol
rt
R = (b) p-C H t-Bu, 15 d
6
4
(
d) n-Pr, 92 h
F
F
F
F
F
F
F
Pp-tol3
Pt
PPhR2
p-tol P
3
F
C
C
C
C
Pt
F
R
PhP
2
F
Pt'C Pt'-b,d
4
R = (b) p-C H t-Bu, 21%
6
4
(
d) n-Pr, 76%
Scheme 6. Syntheses of diplatinum butadiynyl complexes; alternative cross coupling procedure.
-9-

ACCEPTED MANUSCRIPT
Next, comparable conditions were applied to coupling partners that each contained two
different phosphine ligands. As shown in Scheme 6, Pt'C H-b and Pt'Cl-b were reacted for 15 d
4
at room temperature. Workup gave the target complex Pt'C Pt'-b in 21% yield, as well as traces
4
of PtC Pt'-b and Pt'C Pt"-b (ca. 1% each). Considerable amounts of Pt'C H-b and Pt'Cl-b
4
4
4
were recovered (19%, 36%). Comparable conversions were realized after 3-4 d at 50 °C. Finally,
Pt'C H-d and Pt'Cl-d were similarly reacted. Workup after 92 h at room temperature gave the
4
target complex Pt'C Pt'-d in 76% yield after crystallization. No chromatographic purification
4
step was necessary, and no phosphine scrambling byproducts were apparent.
4
. NMR Properties. Certain NMR features of the preceding complexes merit note. In our
8
earlier paper involving similar diplatinum ethynediyl complexes, no coupling was observed be-
5
tween phosphine ligands on opposite termini (small J ). The same would be expected for the
PP
more widely separated phosphine ligands in the diplatinum butadiynediyl complexes in this stu-
7
dy (still smaller J ). Thus, to a first approximation, their NMR spectra should be "hybrids" of
PP
those of the monoplatinum butadiynyl complexes corresponding to each endgroup.
This leads to a hierarchy of complexity. First, there are two "series" of butadiynediyl
complexes with identical endgroups, each with two identical phosphine ligands: PtC Pt (previ-
4
ously reported) and Pt"C Pt"-b (isolated only in trace quantities). These give much simpler
4
spectra. Next, there are the title complexes with identical endgroups, each with two different
1
phosphine ligands: Pt'C Pt'-a-d. The H NMR spectra exhibit the characteristic signals of each
4
phosphine, with only a few cases of resolved second order phenomena. However, the 13C{ H}
1
and 31P{ H} NMR spectra exhibit a variety of second order features as described below. Finally,
1
there are three series of complexes with non-identical endgroups: PtC Pt'-a-c, PtC Pt"-a-c, and
4
4
Pt'C Pt"-a-c. While in theory these give the most complicated NMR spectra, this is only in an
4
additive sense; they seldom introduce new phenomena not manifested in the other complexes.
With regard to the 31P{ H} NMR spectra, certain trends in the monoplatinum complexes
1
deserve comment. First, Pt'Cl-a,d and Pt'C H-a,d feature one triarylphosphine ligand and one
4
dialkylphenylphosphine ligand. They exhibit well separated signals (δ 18.3 to 20.2, p-tol P; –9.9
3
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ACCEPTED MANUSCRIPT
2
to 8.8, R PPh) and couple as expected ( J = 404-450 Hz). However, Pt'Cl-b,c and Pt'C H-b,c
2
PP
4
feature two similar triarylphosphine ligands.18 With Pt'Cl-b and Pt'C H-b, only one singlet is
4
observed (δ 19.8-17.8), presumably due to accidental degeneracy. With Pt'Cl-c and Pt'C H-c,
4
two closely spaced singlets are found (δ 19.51-19.57, 17.58-17.64).
All of these trends extend to the diplatinum butadiynediyl complexes Pt'C Pt'-a-d. How-
4
ever, when 31P{ H} NMR spectra of Pt'C Pt'-b were recorded at –80 °C, separate signals for
1
4
the p-tol P and (p-t-BuC H ) PhP ligands could be observed (δ (CD Cl ) 13.79 and 13.91 as
3
6 4 2
2
2
opposed to one signal at 14.00 at 22 °C). Importantly, the structures of all four complexes have
been confirmed crystallographically (below).
The 13C{ H} NMR spectra of Pt'Cl-a,d, Pt'C H-a,d, and Pt'C Pt'-a,d are unexception-
1
4
4
al. However, those of Pt'Cl-b,c, Pt'C H-b,c, and Pt'C Pt'-b,c are complicated by numerous
4
4
"
virtual couplings".19 That of Pt'C Pt'-b features a variety of virtual triplets (typically 5-6 Hz
4
for all aryl carbon atoms that are o/m to phosphorus). In contrast, that of Pt'C Pt'-c exhibits a
4
corresponding number of doublet of doublets, in which the J values are very close to those of the
virtual triplets. Other complexes that exhibit a large number of virtual triplets include Pt"Cl-a
1
3
1
and Pt"C H-a (nearly all Me PhP ligand C NMR signals, and the Me P H NMR signal).
4
2
2
Many NMR spectra were recorded at low temperature in hopes of detecting dynamic pro-
cesses or separate signals for diastereotopic groups as diagrammed in Scheme 1. All of these
1
were uninformative. For example, the H NMR spectra of Pt'C Pt'-a and Pt'C Pt'-c (CD Cl )
4
4
2
2
1
did not show any significant changes when cooled to −80 °C. In the case of Pt'C Pt'-b, some H
4
NMR peaks became broader, but no decoalescence phenomena were detected. With Pt'C Pt'-
4
b,c, the ipso carbon atoms of the (p-XC H ) P moieties are potentially diastereotopic, but only
6
4 2
broadened 13C{ H, P} signals were observed at –80 °C.
1
31
NMR spectra of the more soluble complex Pt'C Pt'-d were recorded in the lower freez-
4
ing solvent CDFCl2.21 Some H NMR signals merged as the temperature was lowered, but no
decoalescence was apparent at –120 °C. The 13C{ H} NMR spectrum showed only broadening,
and the 31P{ H} NMR spectrum was essentially unchanged.
1
1
1
-11-

ACCEPTED MANUSCRIPT
5
. Structural Properties. Crystal structures were sought as a means of confirming struc-
tural assignments, and for gauging endgroup/endgroup interactions in the diplatinum complexes.
Single crystals of 1, Pt"Cl-e, Pt'C H-a, Pt'C Pt'-a-d, and PtC Pt"-b or solvates thereof were
4
4
4
grown, and the structures were determined as outlined in Tables 1-3 and the experimental sec-
tion. Key metrical parameters are provided in Table 3 and Figures 1-3. Many other tetraphos-
phine complexes with ArPt(C≡C) PtAr linkages have been structurally characterized,2,5a-c,e-l,o-q
m
and the bond lengths and angles in Table 3 are unexceptional.
The molecular structures are depicted in Figures 1-8, and additional representations are
provided below and in the supplementary material. About half of the lattices contained some
type of disorder, which was modeled as detailed in the experimental section. Both Pt'C Pt'-a
4
and Pt'C Pt'-d exhibited centers of inversion at the midpoints of the C chains.
4
4
For the diplatinum complexes, a measure of the "twist" associated with the square planar
endgroups was sought. In one approach, least squares planes were defined using the P-Pt-P link-
age on one terminus, and the platinum from the other. For the idealized atropisomers in Scheme
1
, the angle defined by these two planes would be 90°. As summarized in Table 3, the angles
between the planes in the crystal structures ranged from 0° for the complexes with an inversion
center to 44-51° for the others. When planes defined by the P-Pt-P linkages and the ligating C6F5
carbon atom (Cipso) were employed, the values were very similar.
In the diplatinum complexes, the pentafluorophenyl ligands on each platinum were al-
ways sandwiched between two phosphine derived aryl groups. The average centroid-centroid
spacing (π stacking distance) for each molecule is given in Table 3 (3.60-4.10 Å). This phenome-
non has been seen in many other diplatinum polyynediyl complexes bearing pentafluorophenyl
and two trans-triarylphosphine ligands,2a,c,g,5e,g,k,l and has been attributed to quadrupolar inter-
actions between the fluorinated and non-fluorinated aryl groups.20 Other structural features are
analyzed in the discussion section.
-12-

ACCEPTED MANUSCRIPT
Figure 1. Molecular structure of 1 with thermal ellipsoids at 50% probability level. Key bond lengths (Å) and angles
(
°): Pt(1)-C(15), 2.077(8); Pt(1)-S(1), 2.302(2); Pt(1)-Cl(1), 2.342(2); Pt(1)-P(1), 2.365(2); C(15)-Pt(1)-S(1), 90.4(2);
C(15)-Pt(1)-Cl(1), 86.5(2); S(1)-Pt(1)-Cl(1), 176.26(7); C(15)-Pt(1)-P(1), 177.9(2); S(1)-Pt(1)-P(1), 88.90(7); Cl(1)-
Pt(1)-P(1), 94.35(7).
Figure 2. Molecular structure of Pt"Cl-e with thermal ellipsoids at 50% probability level. Key bond lengths (Å) and
angles (°): Pt(1)-C(1), 2.020(3); Pt(1)-P(2), 2.3634(8); Pt(1)-P(1), 2.3673(8); Pt(1)-Cl(2), 2.3647(7); C(1)-Pt(1)-
P(2), 92.45(8); C(1)-Pt(1)-Cl(2), 168.68(8); P(2)-Pt(1)-Cl(2), 88.52(2); C(1)-Pt(1)-P(1), 90.98(8); P(2)-Pt(1)-P(1),
1
69.14(3); P(1)-Pt(1)-Cl(2), 90.14(3).
-13-

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Figure 3. Molecular structure of Pt'C H-a with thermal ellipsoids at 50% probability level. Key bond lengths (Å)
4
and angles (°): Pt(1)-C(1), 1.993(4); Pt(1)-P(1), 2.3298(13); Pt(1)-P(2), 2.2927(13), Pt(1)-C(5), 2.067(4); C(1)-Pt(1)-
P(2), 88.87(11); C(1)-Pt(1)-C(5), 178.05(17); P(2)-Pt(1)-C(5), 91.37(11); C(1)-Pt(1)-P(1), 90.51(11); P(2)-Pt(1)-
P(1), 179.30(4); P(1)-Pt(1)-C(5), 89.26(11).
Figure 4. Molecular structure of Pt'C Pt'-a with thermal ellipsoids at 50% probability level and solvate molecules
4
omitted.
-14-

ACCEPTED MANUSCRIPT
Figure 5. Molecular structure of Pt'C Pt'-b with thermal ellipsoids at 50% probability level; some t-butyl groups
4
are disordered as described in the experimental section.
Figure 6. Molecular structure of Pt'C Pt'-c with thermal ellipsoids at 50% probability level; the methoxy groups
4
are disordered as described in the experimental section.
-15-

ACCEPTED MANUSCRIPT
Figure 7. Molecular structure of Pt'C Pt'-d with thermal ellipsoids at 50% probability level.
4
Figure 8. Molecular structure of PtC Pt"-b with thermal ellipsoids at 50% probability level and solvate molecules
4
omitted; some t-butyl groups are disordered as described in the experimental section.
-16-

ACCEPTED MANUSCRIPT
6
. Other Characterization. The UV-visible spectra of diplatinum polyynediyl complex-
es have been extensively analyzed as a function of carbon chain length.2a,3a,5g The λmax red
shifts and becomes more intense, and a series of much weaker bands at still longer wavelengths –
representing C≡C vibrational fine structure – become increasingly apparent. Such bands were not
detected when we initially characterized PtC Pt.2a Hence, the UV-visible spectra of representa-
4
tive diplatinum butadiynediyl complexes were recorded at higher concentrations and with special
attention to this region. As summarized in Table 4, two such bands at 395-387 and 428-422 nm
−1
−1
could always be detected. The molar extinction coefficients (
20-50, respectively.
DISCUSSION
. Syntheses. The preceding data reveal a number of synthetic challenges with respect to
both the monoplatinum and diplatinum target complexes. For example, Scheme 3 illustrates the
difficulties associated with introducing two bulky trans t-Bu PhP ligands onto a C F PtCl frag-
ε, M cm ) were 500-400 and
1
■
1
2
6 5
ment. Although a route to the adduct Pt"Cl-e and the substitution product Pt'Cl-e could ulti-
mately be realized, several reactions that worked with less bulky phosphine ligands (Scheme 2)
were unsuccessful. In the same vein, all efforts to replace the chloride ligand in Pt'Cl-e with any
type of alkynyl ligand were thwarted (Scheme 4).
The phosphine ligand scrambling that accompanied the coupling of Pt'C H-a-c and Pt'-
4
Cl-a-c (Scheme 5) was unexpected. This phenomenon was likely masked in earlier studies,
which involved reaction components with a single phosphine ligand.2a,c,d Enhanced substitution
rates are often found with paramagnetic metal complexes.22 Perhaps the copper catalyst some-
how promotes redox equilibria that facilitate scrambling. However, very little or no scrambling is
found with the alternative copper catalyzed coupling protocol in Scheme 6. This recipe was not
investigated until a late stage of this project. Otherwise, at least some of the target complexes
might have been realized in much higher overall yields.
Nonetheless, ligand labilization such as in Scheme 5 can sometimes be turned into an ad-
vantage. For example, one could consider the possibility of carrying out late stage phosphine
-17-

ACCEPTED MANUSCRIPT
substitutions simultaneously with coupling. This could greatly increase the breadth of end prod-
ucts accessible, without a corresponding increase in intermediates that must be characterized.
2
. Structural and Dynamic Properties. None of the low temperature NMR experiments
carried out with the diplatinum butadiynediyl complexes gave any evidence of atropisomerism.
Importantly, the many types of NMR couplings observed at ambient temperature (e.g., 1JPPt
,
nJHPt, J , J , certain J and J , etc.) exclude the operation of any low energy ligand
n
2
n
n
CPt
PP
HP
CP
dissociation processes. These might provide pathways for interconverting atropisomers and/or
exchanging diastereotopic groups (see Scheme 1).
This inability to document atropisomerism could have been anticipated if recently pub-
8
lished studies with related diplatinum ethynediyl complexes had been carried out first. Howev-
er, we misjudged the degree of endgroup/endgroup interactions. In this context, Figure 9 com-
pares space filling representations of three diplatinum complexes: (1) the butadiynediyl complex
2
d
trans,trans-(C F )(Et P) Pt(C≡C) Pt(PEt ) (p-tol), which has four identical, moderately sized
6
5
3
2
2
3 2
phosphine ligands, PEt , (2) Pt'C Pt'-b, which has bulkier p-tol P and (p-t-BuC H ) PhP
3
4
3
6 4 2
ligands on each platinum, and (3) the ethynediyl complex trans,trans-(C F )(p-tol P)(Me PhP)-
6
5
3
2
8
Pt(C≡C)Pt(PPhMe )(Pp-tol )(C F ) (Pt'C Pt'-a), which has a smaller Me PhP ligand and a
2
3
6 5
2
2
bulkier p-tol P ligand on each platinum. The sp carbon chains are highlighted in dark blue.
3
In the first complex (Figure 9, top), the endgroups are well separated and the carbon
chain is highly exposed. In the case of Pt'C Pt'-b (Figure 9, middle), the phosphine ligands on
4
opposite termini have considerable van der Waals contacts, but the carbon chain remains
somewhat visible. With this ligand set, the platinum square planes can apparently rotate by 180°,
allowing the interconversion of the types of structures in Scheme 1. Concomitant gearing of the
aryl groups on the phosphine ligands is required. Space filling representations of all crystallogra-
phically characterized complexes are provided in the supplementary material. Pt'C Pt'-c ex-
4
hibits a slightly higher degree of endgroup/endgroup interactions, but Pt'C Pt'-a,d show no van
4
der Waals contacts as all.
-18-

ACCEPTED MANUSCRIPT
Figure 9. Representative space filling representations of diplatinum polyynediyl complexes: (1) trans,trans-(C F )-
6
5
(
Et P) Pt(C≡C) Pt(PEt ) (p-tol); (2) Pt'C Pt'-b; (3) trans,trans-(C F )(p-tol P)(Me PhP)Pt(C≡C)Pt(PPhMe )(Pp-
3 2 2 3 2 4 6 5 3 2 2
tol )(C F ) (Pt'C Pt'-a).
3
6 5
2
The phosphine ligands on opposite termini in Pt'C Pt'-a (Figure 9, bottom) have extens-
2
ive van der Waals contacts and nearly completely shield the sp carbon chain. However, low tem-
8
perature NMR spectroscopy still failed to establish atropisomerism, presumably due to a modest
barrier to square plane rotation and/or phosphorus substituent gearing. Nonetheless, we consider
this a "near miss", as restricted rotation has been observed about other MC M' linkages (where
2
-19-

ACCEPTED MANUSCRIPT
one metal is formally octahedral).23 Other approaches towards realizing this well established
mode of organic stereoisomerism with square planar metal complexes will be pursued in the fut-
ure. It should also be noted that several other types of atropisomerism have been documented in
inorganic and organometallic complexes,24 and conceptually related types of coordination com-
pounds with only axial chirality have been synthesized.25
3
. Summary. This study has greatly increased the number of diplatinum butadiynediyl
complexes in the literature, particularly with regard to less symmetrically substituted systems.
This was assisted by an unanticipated phosphine ligand scrambling process (Scheme 5), which
proves avoidable under modified reaction conditions (Scheme 6). These complexes and their pre-
cursors exhibit a wealth of fascinating NMR and structural properties. While the diplatinum
complexes remain insufficiently congested for any dynamic processes or atropisomerism to be
observed, other applications can be anticipated (e.g., improved stabilities of mixed valence Pt(II)/
Pt(III) cation radicals)2a,b,g and will be investigated in due course.
■
EXPERIMENTAL SECTION
Reactions were conducted under inert atmospheres. Workups were carried out in air. Tol-
uene and CH Cl used for reactions were dried and degassed with a Glass Contour solvent purif-
2
2
ication system; other solvents were used as received from common commercial sources. The fol-
lowing reagents were used as received: CuCl (99.999%, Aldrich), CuI (99.999%, Aldrich), KPF6
(99.9%, Aldrich), t-BuOK (97.0%, TCI), Cl PhP (98%, Fluka), Me PhP (99%, Strem), n-Pr PhP
2 2 2
(
98%, Aldrich), t-Bu PhP (95%, Aldrich), (p-MeOC H ) PhP (95%, Alfa Aesar), p-tol P (95%,
2
6 4 2
3
TCI) and K PtCl (99.8%, Aldrich).
2
4
NMR spectra were recorded at ambient probe temperature unless noted using a Varian in-
1
13
1
31
1
strument operating at 500.00 ( H), 125.65 ( C{ H}), or 202.28 ( P{ H}) MHz and referenced
1
13
31
as follows (δ/ppm): H, residual internal CHCl (7.26); C, internal CDCl (77.2); P, external
3
3
H PO (0.00). UV/visible spectra were recorded on a Shimadzu UV-1800 spectrophotometer.
3
4
Melting points were recorded using a Stanford Research Systems (SRS) MPA100 (Opti-Melt)
-20-

ACCEPTED MANUSCRIPT
automated melting point system. Microanalyses were conducted by Atlantic Microlab.
1
1
trans-(C F )(Me PhP)(p-tol P)Pt(Cl) (Pt'Cl-a). A Schlenk flask was charged with
6
5
2
3
2
a
trans-(C F )(p-tol P) Pt(Cl) (PtCl; 3.170 g, 3.150 mmol), Me PhP (0.450 mL, 3.150 mmol)
6
5
3
2
2
and CH Cl (140 mL). The mixture was stirred for 16 h. The solvent was removed by rotary eva-
2
2
poration. The residue was washed with hexane (2 × 20 mL) and dried by oil pump vacuum to
give Pt'Cl-a as a white powder (2.344 g, 2.790 mmol, 89%), mp 210 °C. Calcd for C H ClF -
3
5 32
5
P2Pt (840.06): C, 50.04; H, 3.84. Found: 50.01; H, 3.82.
NMR (δ, CDCl ): H 7.53 (m, 2H, o to P, Ph), 7.47 (dd, J = 9.8 Hz, 3JHP = 11.4 Hz,
1
3
3
HH
6
H, o to P, tol), 7.33 (m, 3H, m/p to P, Ph), 7.11 (dd, 3JHH = 8.1 Hz, 4JHP = 1.8 Hz, 6H, m to P,
tol), 2.35 (s, 9H, CH , tol), 1.79 (dd, J = 10.5 Hz, 4JHP = 2.7 Hz, 3JHPt = 36.9 Hz, 6H, P-
2
3
HP
Me ); 13C{ H} 145.9 (dd, J = 229 Hz, 2JCF = 23 Hz, o to Pt, C F ), 140.9 (d, J = 2.3 Hz,
1
1
4
2
CF
6 5
2
CP
p to P, tol), 136.8 (dm, 1JCF = 238 Hz, m/p to Pt, C F ), 134.5 (d, J = 10.4 Hz, o to P, tol),
6 5
CP
1
32.9 (dd, 1JCP = 54 Hz, 3JCP = 3.1 Hz, i to P, Ph), 130.6 (d, 2JCP = 9.7 Hz, o to P, Ph), 130.3
d, 4JCP = 2.0 Hz, p to P, Ph), 128.9 (d, 3JCP = 10.8 Hz, m to P, tol), 128.4 (d, 3JCP = 10.0 Hz, m
(
to P, Ph), 126.6 (dd, 1JCP = 55.4 Hz, 3JCP = 2.7 Hz, 2JCPt = 25.8 Hz,29 i to P, tol), 111.1 (t, 2JCF
1
=
43.5 Hz, i to Pt, C F ), 21.5 (s, CH , tol), 12.3 (dd, J = 36.6 Hz, 3JCP = 1.7 Hz, 2JCPt
=
=
6
5
1
3
CP
2
2
3
4
7.6 Hz,29 PMe2); 31P{ H} 20.2 (d, J = 450 Hz, 1JPPt = 2624 Hz,29 p-tol P), −5.5 (d, J
PP
3
PP
50 Hz, 1JPPt = 2620 Hz,29 PMe Ph).
2
trans-(C F )(Me PhP) Pt(Cl) (Pt"Cl-a). A Schlenk flask was charged with [(C F )-
6
5
2
2
6 5
(
tht)Pt(µ
-Cl)] (1.010 g, 1.040 mmol),26 Me PhP (0.60 mL, 4.20 mmol), and CH Cl (70 mL).
2 2 2 2
The solution was stirred for 18 h and filtered through a celite/decolorizing charcoal/glass frit as-
sembly. The solvent was removed by rotary evaporation. The residue was washed with methanol
(2 × 20 mL) and dried by oil pump vacuum to give Pt"Cl-a as a white powder (0.433 g, 0.643
mmol, 31%). The solvent was removed from the washes by rotary evaporation. The residue was
recrystallized from methanol/hexane mixture to yield another crop of Pt"Cl-a (0.585 g, 0.868
mmol, 42% or 73% total).
NMR (δ, CDCl ): H 7.44 (m, 4H, o to P), 7.32 (m, 6H, m/p to P), 1.73 (virtual t,30 2JHP
1
3
-21-

ACCEPTED MANUSCRIPT
1
1
=
3.9 Hz, 3JHPt = 27.9 Hz, 12H, Me); 13C{ H} 146.3 (dd, J = 228 Hz, 2JCF = 26 Hz, 2JCPt
=
=
CF
1
7
2
1
6 Hz,29 o to Pt, C F ), 136.6 (dm, J = 247 Hz, m/p to Pt, C F ), 132.6 (virtual t,30 1JCP
6
5
CF
6 5
8.1 Hz, 2JCPt = 33.2 Hz,29 i to P), 130.4 (virtual t,30 2JCP = 5.8 Hz, o to P), 130.3 (s, p to P),
28.4 (virtual t,30 3JCP = 5.1 Hz, m to P), 108.1 (t, 2JCF = 43.5 Hz, i to Pt, C F ), 12.2 (virtual
6 5
t,30 1JCP = 18.9 Hz, 2JCPt = 35.8 Hz,29 PMe2); 31P{ H} −5.5 (s, J = 2520 Hz29).
1
1
PPt
trans-(C F )(p-tol P)((p-t-BuC H ) PhP)Pt(Cl) (Pt'Cl-b). A Schlenk flask was charg-
6
5
3
6 4 2
2
a
27
ed with PtCl (6.186 g, 6.147 mmol), (p-t-BuC H ) PhP (2.302 g, 6.147 mmol), and toluene
6
4 2
(150 mL). The solution was refluxed for 22 h. The solvent was removed by rotary evaporation
and oil pump vacuum. The residue was washed with hexane (3 × 30 mL, leaving 5.213 g) and
chromatographed on a silica gel column (3.8 × 42 cm, 8:1 v/v toluene/hexane). The solvent was
removed from the product containing fractions by rotary evaporation and oil pump vacuum to
give Pt'Cl-b (1.906 g, 1.771 mmol, 29%), PtCl (1.475 g, 1.466 mmol, 24%), and an unknown
complex (0.121 g) as white solids. A fourth fraction contained mainly trans-(C F )((p-t-BuC -
6
5
6
H ) PhP) Pt(Cl) (Pt"Cl-b, ∼ 10%), together with the unknown complex and a second one.
4
2
2
Date for Pt'Cl-b. dec pt 249 °C. Calcd. for C H ClF P Pt (1076.46): C 59.14, H 4.87.
5
3 52
5 2
1
Found: C 59.31, H 4.86. NMR (δ, CDCl ): H 7.88-7.78 (m, 2H, o to P, Ph), 7.60-7.47 (m, 10H,
3
3
o to P, tol+C H ), 7.40-7.33 (m, 3H, m/p to P, Ph), 7.30 (d, J
= 8.4 Hz, 4H, m to P, C6H4),
6
4
HH
13
1
7
1
.13 (d, 3JHH = 7.8 Hz, 6H, m to P, tol), 2.36 (s, 9H, CH , tol), 1.30 (s, 18H, C(CH ) ); C{ H}
3 3 3
1
2
53.9 (s, p to P, C H ), 145.3 (dd, J = 225 Hz, J = 22 Hz, o to Pt, C F ), 141.0 (s, p to P,
6
4
CF
CF
6 5
tol), 136.3 (dm, 1JCF = 245 Hz, m/p to Pt, C F ), 135.0 (virtual t,30 2JCP = 6.3 Hz, o to P, Ph),
6 5
1
1
34.6 (virtual t,30 2JCP = 6.3 Hz, o to P, tol), 134.3 (virtual t,30 2JCP = 6.3 Hz, o to P, C6H4),
30.7 (s, p to P, Ph), 130.2 (dd, 1JCP = 30.9 Hz, 3JCP = 26.5 Hz, i to P, Ph), 128.9 (virtual t,30
3JCP = 5.7 Hz, m to P, tol), 128.2 (virtual t,30 3JCP = 5.6 Hz, m to P, Ph), 126.7 (dd, 1JCP = 31.7
Hz, 3JCP = 27.5 Hz, i to P, tol), 126.6 (dd, 1JCP = 31.8 Hz, 3JCP = 27.2 Hz, i to P, C H ), 125.1
6 4
virtual t,30 3JCP = 5.6 Hz, m to P, C H ), 114.5 (t, J = 45.4 Hz, i to Pt, C F ), 34.9 (s,
2
(
6 4
CF
6 5
C(CH ) ), 31.2 (s, CH ); 21.5 (s, CH , tol); P{ H} 19.8 (s, J = 2726 Hz29).
3
1
1
1
3
3
3
3
PPt
trans-(C F )((p-t-BuC H ) PhP) Pt(Cl) (Pt"Cl-b). A Schlenk flask was charged with
6
5
6
4 2
2
-22-

ACCEPTED MANUSCRIPT
(C F )(tht)Pt(µ
-Cl)] (0.129 g, 0.132 mmol),26 (p-t-BuC H ) PhP (0.218 g, 0.582 mmol),
6 5
27
[
2
6 4 2
and CH Cl (20 mL). The solution was stirred for 16 h and filtered through a celite/decolorizing
2
2
charcoal/glass frit assembly. The solvent was removed by rotary evaporation. The residue was
washed with cold methanol (2 × 10 mL) and dried by oil pump vacuum to give Pt"Cl-b as a
white powder (0.231 g, 0.201 mmol, 76%).
1
NMR (δ, CDCl ): H 7.91-7.80 (m, 4H, o to P, Ph), 7.56-7.46 (m, 8H, o to P, C H ),
3
6 4
7
.44-7.36 (m, 6H, m/p to P, Ph), 7.28 (d, 3JHH = 8.4 Hz, 8H, m to P, C H ), 1.29 (s, 36H, CH );
6 4 3
3
1
1
1
= 2731 Hz29).
P{ H} 19.7 (s, J
PPt
trans-(C F )(p-tol P)((p-MeOC H ) PhP)Pt(Cl) (Pt'Cl-c). A Schlenk flask was charg-
6
5
3
6 4 2
ed with PtCl (5.032 g, 5.000 mmol),2a (p-MeOC H ) PhP (1.612 g, 5.000 mmol), and toluene
6
4 2
(
120 mL). The solution was refluxed for 22 h. The solvent was removed by rotary evaporation
and oil pump vacuum. The residue was washed with hexane (3 × 50 mL) and chromatographed
on a silica gel column (3.8 × 42 cm), using 50:50 v/v CH Cl /hexane to elute PtCl, 80:20 v/v
2
2
CH Cl /hexane to elute Pt'Cl-c, and 40:60 v/v ethyl acetate/hexane to elute trans-(C F )((p-Me-
2
2
6 5
OC H ) PhP) Pt(Cl) (Pt"Cl-c). The solvent was removed from the fractions by rotary evapora-
6
4 2
2
tion and oil pump vacuum to give PtCl (1.406 g, 1.397 mmol, 28%), Pt'Cl-c (2.149 g, 2.098
mmol, 42%) and Pt"Cl-c (0.643 g, 0.616 mmol, 13%) as white solids.
Data for Pt'Cl-c. mp 215 °C. Calcd for C H ClF O P Pt (1024.30): C, 55.11; H, 3.94.
4
7 40
5 2 2
1
Found: 55.06; H, 3.95. NMR (δ, CDCl ): H 7.71-7.61 (m, 4H, o to P, C H ), 7.59-7.42 (m, 8H,
3
6 4
o to P, tol+Ph), 7.37-7.29 (m, 1H, p to P, Ph), 7.26 (d, 3JHH = 7.2 Hz, 2H, m to P, Ph), 7.13 (d,
3JHH = 7.5 Hz, 6H, m to P, tol), 6.88 (d, 3JHH = 8.1 Hz, 4H, m to P, C H ), 3.83 (s, 6H, OCH ),
6 4
3
.36 (s, 9H, CH , tol); C{ H} 161.5 (s, p to P, C H ), 145.2 (dd, J = 225 Hz, 2JCF = 20 Hz,
1
3
1
1
2
3 6 4 CF
1
o to Pt, C F ), 140.9 (s, p to P, tol), 136.5 (dm, J = 238 Hz, m/p to Pt, C F ), 136.4 (virtual
6
5
CF
6 5
t,30 2JCP = 6.9 Hz, o to P, C H ), 134.4 (virtual t,30 2JCP = 6.3 Hz, o to P, tol), 133.7 (virtual t,30
6 4
2JCP = 5.9 Hz, o to P, Ph), 131.0 (dd, 1JCP = 33.9 Hz, 3JCP = 23.9 Hz, i to P, Ph), 130.2 (s, p to
P, Ph), 128.8 (virtual t,30 3JCP = 5.5 Hz, m to P, tol), 127.8 (virtual t,30 3JCP = 5.2 Hz, m to P,
Ph), 126.5 (dd, 1JCP = 34.4 Hz, 3JCP = 24.7 Hz, i to P, tol), 120.5 (dd, 1JCP = 36.6 Hz, 3JCP
=
-23-

ACCEPTED MANUSCRIPT
5.9 Hz, i to P, C H ), 114.5 (br, i to Pt, C F ), 113.8 (dd, J = 6.6 Hz, 5JCP = 5.1 Hz, m to P,
3
2
6
4
6 5
CP
C H ), 55.4 (s, OCH ), 21.4 (s, CH , tol); P{ H} 19.565, 19.506 (2 × s, J = 2723 Hz29).
3
1
1
1
6
4
3
3
PPt
trans-(C F )((p-MeOC H ) PhP) Pt(Cl) (Pt"Cl-c). A Schlenk flask was charged with
6
5
6
4 2
2
[
(C F )(tht)Pt(µ
-Cl)] (0.140 g, 0.144 mmol),26 (p-MeOC H ) PhP (0.210 g, 0.652 mmol), and
6 5 2 6 4 2
CH Cl (25 mL). The solution was stirred for 16 h and filtered through a celite/decolorizing
2
2
charcoal/glass frit assembly. The solvent was removed by rotary evaporation. The residue was
washed with methanol (2 × 2 mL) and recrystallized from dichloromethane/hexane/methanol to
give Pt"Cl-c as a white powder (0.155 g, 0.149 mmol, 52%).
1
NMR (δ, CDCl ): H 7.71-7.60 (m, 8H, o to P, C H ), 7.54-7.43 (m, 4H, o to P, Ph),
3
6 4
7
8
.38-7.30 (m, 6H, p to P, Ph), 7.26 (d, 3JHH = 7.5 Hz, 4H, m to P, Ph), 6.88 (d, 3JHH = 8.7 Hz,
H, m to P, C H ), 3.83 (s, 12H, OCH ); P{ H} 19.2 (s, J = 2716 Hz29).
31
1
1
6
4
3
PPt
trans-(C F )(p-tol P)(n-Pr PhP)Pt(Cl) (Pt'Cl-d). A Schlenk flask was charged with
6
5
3
2
2
a
PtCl (6.167 g, 6.128 mmol), n-Pr PhP (1.30 mL, 6.190 mmol), and toluene (120 mL). The sol-
2
ution was stirred for 16 h and then refluxed for 6 h. The solvent was removed by rotary evapora-
tion and oil pump vacuum. The residue was washed with hexane (3 × 60 mL). Only unreacted
PtCl remained (1.096 g, 1.089 mmol, 18%). The solvent was removed from the combined wash-
es by rotary evaporation and oil pump vacuum. The residue was chromatographed on a silica gel
column (6.4 × 43 cm) using 50:50 v/v CHCl /hexane to elute displaced p-tol P, 55:45 v/v CHCl
3
3
3
/
hexane to elute Pt"Cl-d, 60:40 v/v CHCl /hexane to elute Pt'Cl-d, and 80:20 v/v CHCl /hex-
3 3
ane to elute PtCl. The solvent was removed from the fractions by rotary evaporation and oil
pump vacuum to give Pt"Cl-d (0.481 g, 0.612 mmol, 10%), Pt'Cl-d (2.295 g, 2.561 mmol,
4
2%), and PtCl (0.511 g, 0.508 mmol, 9% or 27% including the residue isolated above).
Data for Pt'Cl-d. NMR (δ, CDCl ): H 7.47 (dd, J = 11.0 Hz, 3JHH = 8.0 Hz, 6H, o
1
3
3
HP
to P, tol; overlapped with m, 2H, o to P, Ph), 7.35-7.28 (m, 3H, m/p to P, Ph), 7.10 (dd, 3JHH
=
8
1
1
.0 Hz, 4JHP = 2.0 Hz, 6H, m to P, tol), 2.35 (s, 9H, CH , tol), 2.29-1.95 (m, 4H, PCH ), 1.79-
3
2
.39 (m, 4H, PCH CH ), 1.01 (dt, J = 7.5 Hz, 4JHP = 0.5 Hz, 6H, PCH CH CH ); C{ H}
3
13
1
2
2
HH
2
2
3
45.8 (dd, 1JCF = 226 Hz, 2JCF = 19 Hz, o to Pt, C F ), 140.8 (d, J = 2.5 Hz, p to P, tol),
4
6 5
CP
-24-

ACCEPTED MANUSCRIPT
36.6 (dm, 1JCF = 256 Hz, m/p to Pt, C F ), 134.4 (dd, J = 11.1 Hz, 4JCP = 1.1 Hz, o to P,
2
1
6 5
CP
tol), 131.3 (d, 2JCP = 8.8 Hz, o to P, Ph), 130.6 (dd, 1JCP = 50.0 Hz, 3JCP = 2.6 Hz, i to P, Ph),
30.0 (d, 4JCP = 2.4 Hz, p to P, Ph), 128.8 (d, 3JCP = 10.9 Hz, m to P, tol), 128.2 (d, 3JCP = 9.8
Hz, m to P, Ph), 126.6 (dd, 1JCP = 55.0 Hz, 3JCP = 3.0 Hz, i to P, tol), 111.1 (t, 2JCF = 43.8 Hz, i
1
to Pt, C F ), 24.9 (dd, J = 32.0 Hz, 3JCP = 1.9 Hz, PCH ), 21.4 (d, J = 1.1 Hz, CH , tol),
1
5
6
5
CP
2
CP
3
3
31
1
2
1
7.7 (s, PCH CH ), 15.9 (d, J = 14.7 Hz, PCH CH CH ); P{ H} 20.2 (d, J = 434 Hz,
2 2 CP 2 2 3 PP
1JPPt = 2624 Hz,29 p-tol P), 8.8 (d, J = 434 Hz, 1JPPt = 2629 Hz,29 n-Pr PhP).
2
3
PP
2
trans-(C F )(n-Pr PhP) Pt(Cl) (Pt"Cl-d). A Schlenk flask was charged with [(C F )-
6
5
2
2
6 5
2
6
(
tht)Pt(µ-Cl)] (0.130 g, 0.134 mmol), n-Pr PhP (0.13 mL, 0.619 mmol) and CH Cl (25 mL).
2 2 2 2
The solution was stirred for 16 h and filtered through a celite/decolorizing charcoal/glass frit
assembly. The solvent was removed by rotary evaporation. The residue was recrystallized from
hexane to give Pt"Cl-d as a white powder (0.125 g, 0.159 mmol, 60%).
1
4
NMR (δ, CDCl ): H 7.43-7.37 (m, 4H, o to P), 7.29 (d, J = 7.0 Hz, 4H, m to P,
3
HP
overlapped with m, 2H, p to P), 2.21-1.90 (m, 8H, PCH ), 1.71-1.33 (m, 8H, PCH CH ), 0.98 (t,
2
2
2
3JHH = 7.5 Hz, 12 H, PCH CH CH ); P{ H} 8.7 (s, J = 2534 Hz29).
31
1
1
2
2
3
PPt
3
1
(
C F )(t-Bu PhP)(tht)Pt(Cl) (1). A Schlenk flask was charged with [(C F )(tht)Pt(µ-
6 5 2 6 5
2
6
Cl)] (0.986 g, 1.015 mmol), t-Bu PhP (1.16 mL, 4.816 mmol), and CH Cl (75 mL). The so-
2
2
2
2
lution was stirred for 16 h and filtered through a celite/decolorizing charcoal/glass frit assembly.
The solvent was removed by rotary evaporation. The residue was washed with cold methanol (2
×
10 mL). Recrystallization from CH Cl /hexane gave colorless crystals of 1 (1.099 g, 1.552
2 2
mmol, 77%).
1
NMR (δ, CDCl ): H 7.99-7.88 (m, 4H, o to P), 7.52-7.43 (d, 6H, m/p to P), 3.04, 2.71
3
3
(
each br, 4H, SCH ), 1.59 (d, 18H, J
= 13.5 Hz, C(CH ) ), 1.42 (br, 4H, SCH CH ) ;
2
HP 3 3 2 2
1
3
C{ H} 146.7 (dd, 1JCF = 222 Hz, 2JCF = 22 Hz, o to Pt, C F ), 137.6 (dm, J = 243 Hz,
1
32
1
6 5
CF
m/p to Pt, C F ), 135.2 (d, J = 8.4 Hz, o to P), 131.2 (d, 1JCP = 35.3 Hz, i to P), 130.3 (d,
2
6
5
CP
4JCP = 2.0 Hz, p to P), 127.9 (d, 3JCP = 8.7 Hz, m to P), 39.4 (s, SCH ), 37.5 (d, J = 18.6 Hz,
1
2
CP
2JCPt = 17.7 Hz,29 C(CH ) ), 30.9 (d, J
2
3
= 15.9 Hz,29
= 3.0 Hz, CH ), 29.8 (s, J
3 CPt
3 3
CP
-25-

ACCEPTED MANUSCRIPT
SCH CH ); P{ H} (see Figure S4) 42.0 (apparent septet, J = 34.8 Hz, 1JPPt = 2330 Hz29).
3
1
1
4
2
2
PF
1
2,14
trans-(t-Bu PhP) Pt(Cl) (2).
A Schlenk flask was charged with K PtCl (1.299 g,
2 4
2
2
2
3
.130 mmol) and deoxygenated H O (10 mL). Another Schlenk flask was charged with t-Bu Ph-
2 2
P (1.50 mL, 6.295 mmol) and ethanol (10 mL). The ethanol solution was transferred via cannula
to the aqueous solution. The resulting pink suspension was stirred. After 1 d, the yellow precipi-
tate was washed with H O, ethanol, hexane and diethyl ether, and dried in vacuum to give
2
previously reported 2 (1.968 g, 2.769 mmol, 89%).
1
NMR (δ, CDCl ): H 7.94 (br, 4H, o to P, Ph), 7.42-7.30 (m, 6H, m/p to P, Ph), 1.61
3
virtual t,30 3JHP = 6.8 Hz, 36H, C(CH3)3); 31P{ H} 42.8 (s, J = 2542 Hz29).
1
1
(
PPt
trans-(C F )(t-Bu PhP) Pt(Cl) (Pt"Cl-e). A Schlenk flask was charged with (cod)(C -
6
5
2
2
6
F5)Pt(Cl) (2.797 g, 5.530 mmol),16 t-Bu PhP (3.50 mL, 14.689 mmol) and toluene (120 mL).
2
The solution was refluxed for 48 h. The solvent was removed by rotary evaporation and oil pump
vacuum. The residue was washed with ethanol (2 × 25 mL) and hexane (2 × 25 mL) and dried by
oil pump vacuum to give Pt"Cl-e as a white solid (2.980 g, 3.538 mmol, 64%).
1
NMR (δ, CDCl ): H 7.90 (br, s, 4H, o to P, Ph), 7.24-7.08 (m, 6H, m/p to P, Ph), 1.58 (t,
3
3JHP = 6.0 Hz, 36H, C(CH3)3); 31P{ H} 41.8 (br s, J = 2668 Hz).
1
1
PPt
trans-(C F )(p-tol P)(t-Bu PhP)Pt(Cl) (Pt'Cl-e). A Schlenk flask was charged with
6
5
3
2
Pt"Cl-e (2.815 g, 3.342 mmol), p-tol P (1.025 g, 3.368 mmol) and toluene (120 mL). The solu-
3
tion was refluxed for 14 h. The solvent was removed by rotary evaporation. The residue was
washed with methanol (2 × 30 mL), ethanol (20 mL) and hexane (20 mL) to give Pt'Cl-e as a
white powder (2.800 g, 3.029 mmol, 91%).
NMR (δ, CDCl ): H 7.87-7.80 (m, 2H, o to P, Ph), 7.52 (dd, J = 11.0 Hz, 3JHH = 8.0
1
3
3
HP
Hz, 6H, o to P, tol), 7.28-7.21 (m, 3H, m/p to P, Ph), 7.11 (d, 3JHH = 8.0 Hz, 4JHP = 2.0 Hz, 6H,
m to P, tol), 2.35 (s, 9H, CH , tol) 1.52 (d, J = 14.0 Hz, 18H, C(CH3)3); 13C{ H} 146.2 (dd,
3
1
3
HP
1JCF = 222 Hz, 2JCF = 20 Hz, o to Pt, C F ), 140.8 (d, J = 2.4 Hz, p to P, tol), 136.8 (dm,
4
6 5
2
CP
1JCF = 254 Hz, m/p to Pt, C F ), 135.5 (d, J = 7.9 Hz, o to P, Ph), 134.6 (d, 2JCP = 10.7 Hz, o
6 5
CP
to P, tol), 130.1 (d, 1JCP = 38.3 Hz, i to P, Ph), 129.6 (d, 4JCP = 1.6 Hz, p to P, Ph), 128.7 (d,
-26-

ACCEPTED MANUSCRIPT
3JCP = 11.2 Hz, m to P, tol), 126.7 (d, 3JCP = 9.0 Hz, m to P, Ph), 126.7 (dd, 1JCP = 58.3 Hz,
3JCP = 1.8 Hz, i to P, tol), 111.0 (t, 2JCF = 40.2 Hz, i to Pt, C F ), 37.6 (dd, J = 17.8 Hz, 3JCP
1
6 5
CP
3.0 Hz, C(CH )), 31.5 (s, CH ); 21.5 (s, CH , tol); P{ H} 50.2 (d, J = 421 Hz, 1JPPt
3
1
1
2
=
=
3 3 3 PP
711 Hz,29 t-Bu PhP), 18.5 (d, J = 421 Hz, 1JPPt = 2689 Hz,29 p-tol P).
2
2
2 PP 3
trans-(C F )(Me PhP)(p-tol P)Pt(C≡C) H (Pt'C H-a). Synthesis A. A Schlenk flask
6
5
2
3
2
4
2a
was charged with trans-(C F )(p-tol P) Pt(C≡C) H (PtC H; 0.822 g, 0.806 mmol), Me PhP
6
5
3
2
2
4
2
(
0.115 mL, 0.811 mmol), and CH Cl (60 mL). The solution was stirred for 18 h. The solvent
2 2
was removed by oil pump vacuum. The residue was washed with hexane (2 × 20 mL). A 31P
{1
H} NMR spectrum of the washes showed signals for p-tol P, p-tol PO, and smaller quantities
of platinum complexes (∼ 10%). The residue was chromatographed on a silica gel column (2.5 ×
0 cm, packed in hexane, eluted with 1:1 v/v CH Cl /hexane). The solvent was removed from
3
3
3
2
2
the product containing fractions by rotary evaporation and oil pump vacuum to give PtC H as an
4
off-white solid (0.148 g, 0.145 mmol, 18%), Pt'C H-a as pale yellow solid (0.206 g, 0.242
4
mmol, 30%), and trans-(C F )(Me PhP) Pt(C≡C) H (Pt"C H-a) as a pale yellow solid (0.061
6
5
2
2
2
4
g, 0.089 mmol, 11%).
Data for Pt'C H-a. mp 128 °C. Calcd for C H F P Pt (853.71): C, 54.87; H, 3.90.
4
39 33 5 2
1
3
Found: 54.66; H, 3.90. NMR (δ, CDCl ): H 7.53 (m, 2H, o to P, Ph), 7.45 (dd, J = 8.3 Hz,
3
HH
3JHP = 11.6 Hz, 6H, o to P, tol), 7.35 (m, 3H, m/p to P, Ph), 7.11 (dd, 3JHH = 7.8 Hz, 4JHP = 1.8
Hz, 6H, m to P, tol), 2.36 (s, 9H, CH , tol), 1.88 (dd, J = 10.5 Hz, 4JHP = 2.7 Hz, 3JHPt
2
=
3
HP
4.4 Hz,29 6H, PMe ), 1.69 (t, J = 1.0 Hz, 5JHPt = 9.3 Hz,29 1H, ≡CH); 13C{ H} 146.4 (dd,
6
1
4
2 HP
1JCF = 228 Hz, 2JCF = 22 Hz, o to Pt, C F ), 140.9 (d, J = 2.3 Hz, p to P, tol), 136.9 (dm,
4
6 5
2
CP
1JCF = 230 Hz, m/p to Pt, C F ), 134.4 (d, J = 10 Hz, 3JCPt = 31 Hz,29 o to P, tol), 133.5 (dd,
6 5
CP
1JCP = 54.4 Hz, 3JCP = 3.1 Hz, 2JCPt = 28.9 Hz,29 i to P, Ph), 130.7 (d, 2JCP = 9.7 Hz, 3JCPt
=
2
8.2 Hz,29 o to P, Ph), 130.4 (d, 4JCP = 2.3 Hz, p to P, Ph), 128.9 (d, 3JCP = 11.1 Hz, m to P,
tol), 128.4 (d, 3JCP = 10.4 Hz, m to P, Ph), 127.4 (dd, 1JCP = 56.8 Hz, 3JCP = 2.6 Hz, 2JCPt
=
7.2 Hz,29 i to P, tol), 124.5 (t, 2JCF = 52 Hz, i to Pt, C F ), 99.5 (br, J
1
= 1011 Hz,29 Pt-
CPt
2
6 5
C≡C), 92.7 (s, 2JCPt = 278 Hz,29 PtC≡C), 72.4 (t, 4JCP = 2.3 Hz, 3JCPt = 36.7 Hz,29 PtC≡CC),
-27-

ACCEPTED MANUSCRIPT
0.1 (s, PtC≡CC≡C), 21.5 (s, CH , tol), 14.4 (dd, J = 37.6 Hz, 3JCP = 1.7 Hz, 2JCPt = 45.3
1
6
3
CP
Hz,29 PMe2); 31P{ H} 18.3 (d, J = 419 Hz, 1JPPt = 2556 Hz,29 p-tol P), −9.9 (d, J = 419
1
2
2
PP
3
PP
Hz, 1JPPt = 2529 Hz,29 Me PhP).
2
1
3
Data for Pt"C H-a. NMR (δ, CDCl ): H 7.44 (m, 4H, o to P, Ph), 7.34 (t, J = 0.9
4
3
HP
Hz, 4H, m to P, Ph), 7.32 (m, 2H, p to P, Ph), 1.82 (virtual t,30 2JHP = 3.9 Hz, 3JHPt = 33 Hz,
2H, PMe ; ≡CH signal not observed); 13C{ H} 146.7 (dd, 1JCF = 216 Hz, 2JCF = 28 Hz, o to
1
32
1
2
Pt, C F ), 136.8 (dm, J = 258 Hz, m/p to Pt, C F ), 133.2 (virtual t,30 1JCP = 28.6 Hz, i to P),
1
6
5
CF
6 5
1
30.6 (virtual t,30 2JCP = 5.8 Hz, o to P), 130.4 (s, p to P), 128.5 (virtual t,30 3JCP = 5.1 Hz, m to
P), 100.2 (br, PtC≡C), 90.3 (s, 2JCPt = 256 Hz,29 PtC≡C), 72.2 (s, PtC≡CC), 60.2 (s, PtC≡C-
C≡C), 14.3 (virtual t,30 1JCP = 19.8 Hz, 2JCPt = 44.3 Hz,29 PMe2); 31P{ H} −9.9 (s, J
1
1
=
PPt
2
9
2
426 Hz ).
Synthesis B. A Schlenk flask was charged with Pt'Cl-a (0.791 g, 0.942 mmol), CuI
0.040 g, 0.21 mmol), CH Cl (6 mL), and HNEt (50 mL), and cooled to −45 °C (CO /CH -
(
2
2
2
2
3
CN). Then butadiyne (1.7 M in THF, 10.5 mL, 17.5 mmol)28 was added with stirring. The cold
bath was allowed to warm to room temperature (ca. 3 h). After an additional 16 h, the solvent
was removed by oil pump vacuum. The residue was extracted with toluene (3 × 20 mL). The
combined extracts were filtered through a neutral alumina column (7 cm, packed in toluene). The
solvent was removed by rotary evaporation and oil pump vacuum. The residue was washed with
ethanol (20 mL) and dried by oil pump vacuum (total mass 0.5015 g). Analysis by 31P{ H}
1
NMR established the following product quantities: Pt'C H-a (0.2835 g, 0.332 mmol, 36%), Pt-
4
C H (0.154 g, 0.151 mmol, 16%), Pt"C H-a (0.064 g, 0.093 mmol, 10%).
4
4
trans-(C F )(p-tol P)((p-t-BuC H ) PhP)Pt(C≡C) H (Pt'C H-b). A Schlenk flask was
6
5
3
6
4 2
2
4
charged with Pt'Cl-b (0.539 g, 0.501 mmol), CuI (0.020 g, 0.11 mmol), CH Cl (4 mL) and
2
2
HNEt (40 mL), and cooled to −45 °C (CO /CH CN). Then butadiyne (2.14 M in THF, 4.2 mL,
2
2
3
9
.0 mmol)28 was added with stirring. The cold bath was allowed to warm at 10 °C (ca. 6 h). The
cold bath was removed, and after an additional 1 h, the solvent was removed by oil pump vacu-
um. The residue was extracted with toluene (3 × 25 mL). The combined extracts were filtered
-28-

ACCEPTED MANUSCRIPT
through a neutral alumina column (2.5 × 7 cm, packed in toluene). The solvent was removed by
rotary evaporation to give Pt'C H-b as an off-white solid (0.418 g, 0.384 mmol, 77%), dec pt
4
1
4
49 °C. Calcd for (C H F P Pt)⋅(CH Cl ) (1175.03): C, 59.29; H, 4.72. Found: 59.16; H,
57 53 5 2 2 2
.72.
1
NMR (δ, CDCl ): H 7.85-7.73 (m, 2H, o to P, Ph), 7.62-7.41 (m, 10H, o to P, tol+C -
3
6
3
3
H ), 7.43-7.34 (m, 3H, m/p to P, Ph), 7.29 (d, J = 8.4 Hz, 4H, m to P, C H ), 7.12 (d, J
=
4
HH
6 4
HH
6
7
.8 Hz, 6H, m to P, tol), 5.31 (s, 2H, CH Cl ), 2.35 (s, 9H, CH , tol), 1.47 (t, J = 0.9 Hz, 1H,
2
2
3
HP
CH); 1.29 (s, 18H, C(CH ) ); C{ H} 154.0 (s, p to P, C H ), 146.0 (dd, J = 226 Hz, 2JCF
1
3
1
1
≡
3
3
6 4
CF
1
=
23 Hz, o to Pt, C F ), 141.0 (s, p to P, tol), 136.5 (dm, J = 254 Hz, m/p to Pt, C F ), 134.9
6 5 CF 6 5
(
virtual t,30 2JCP = 6.4 Hz, o to P, Ph), 134.6 (virtual t,30 2JCP = 6.4 Hz, o to P, tol), 134.3 (vir-
tual t,30 2JCP = 6.4 Hz, o to P, C H ), 131.1 (virtual t,30 1JCP = 29.3 Hz, i to P, Ph), 130.7 (s, p
6 4
to P, Ph), 128.9 (virtual t,30 3JCP = 5.6 Hz, m to P, tol), 128.2 (virtual t,30 3JCP = 5.5 Hz, m to P,
Ph), 127.5 (virtual t,30 1JCP = 30.2 Hz, i to P, tol), 127.2 (virtual t,30 1JCP = 30.0 Hz, i to P, C6-
H ), 125.1 (virtual t,30 3JCP = 5.5 Hz, m to P, C H ), 98.1 (s, J
1
= 993 Hz,29 PtC≡C), 95.3 (s,
4
6 4
CPt
2JCPt = 265 Hz,29 PtC≡C), 72.7 (t, 4JCP = 2.5 Hz, 3JCPt = 36.2 Hz,29 PtC≡CC), 59.9 (s, PtC≡C-
3
1
1
C≡C), 53.7 (s, CH Cl ), 34.9 (s, C(CH ) ), 31.3 (s, CH ); 21.5 (s, CH , tol); P{ H} 17.8 (s,
2
2
3 3
3
3
1JPPt = 2656 Hz29).
trans-(C F )(p-tol P)((p-MeOC H ) PhP)Pt(C≡C) H (Pt'C H-c). Complex Pt'Cl-c
6
5
3
6
4 2
2
4
(
1.317 g, 1.286 mmol), CuI (0.051 g, 0.268 mmol), CH Cl (10 mL), HNEt (80 mL), and buta-
2 2 2
diyne (2.14 M in THF, 15 mL, 32.1 mmol)28 were combined in a procedure analogous to that for
Pt'C H-b. A similar workup (toluene extraction 3 × 40 mL) gave Pt'C H-c as an off-white solid
4
4
(
0.999 g, 0.962 mmol, 75%), mp 138 °C. Calcd for C H F O P Pt (1037.92): C, 59.02; H,
51 41 5 2 2
3
.98. Found: 58.93; H, 3.98.
1
NMR (δ, CDCl ): H 7.66-7.56 (m, 4H, o to P, C H ), 7.55-7.41 (m, 8H, o to P, tol+Ph),
3
6 4
7
6
.36-7.29 (m, 1H, p to P, Ph), 7.26 (d, 3JHH = 5.4 Hz, 2H, m to P, Ph), 7.12 (d, 3JHH = 7.5 Hz,
H, m to P, tol), 6.87 (d, 3JHH = 9.0 Hz, 4H, m to P, C H ), 3.84 (s, 6H, OCH ), 2.36 (s, 9H,
6 4
3
CH , tol), 1.49 (t, J = 0.9 Hz, 1H, ≡CH); 13C{ H} 161.6 (s, p to P, C H ), 145.9 (dd, J
=
CF
6
1
1
3
HP
6 4
-29-